ES2742100T3 - Olefin polymer prepared by a catalytic system with three metallocenes - Google Patents

Abstract

An olefin polymer having a melt index in a range of 0.005 to 10 g / 10 min, determined according to ASTM-1238 at 190 ° C with a weight of 2,160 grams, an IFAC / IF ratio in a range of 50 to 500, wherein IFAC is determined according to ASTM-1238 at 190 ° C with a weight of 21,600 grams, a density in a range of 0.915 g / cm3 to 0.965 g / cm3 determined according to ASTM-1505 and ASTM-1928, procedure C, as described in the description, a non-bimodal molecular weight distribution and an inverse comonomer distribution both determined by GPC as described in the description.

Description

DESCRIPTION

Olefin polymer prepared by a catalytic system with three metallocenes

Background of the invention

Polyolefins, such as a high density polyethylene homopolymer (HDPE) and a linear low density polyethylene copolymer (LLDPE), can be produced using various combinations of catalyst systems and polymerization processes. Chromium-based and Ziegler-based catalyst systems can produce, for example, polymer resins with good processability, typically due to their wide molecular weight distribution (DPM). In contrast, polymers produced using catalytic systems containing a single metallocene compound generally have a narrow DPM and, accordingly, poor processability. The broad DPM and bimodal resins can be prepared from double metallocene catalyst systems. However, bimodal resins of broad DPM may experience treatment problems, such as a fracture of fusion, due to the disparity of molecular weights of the two components of the DPM. In addition, chromium-based and Ziegler-based catalyst systems often produce polymers in which there is more of the comonomer in the fraction of the polymer's lower molecular weight. The presence of more comonomer in the higher molecular weight fraction of the polymer, often referred to as an inverse comonomer distribution or an inverse short chain branching distribution (DRCC), can often improve physical properties in various end-use applications. .

In view of these generalities, it would be beneficial to produce polymers of wide molecular weight distribution with inverse comonomer or inverse DRCC. Accordingly, the present invention refers to these purposes.

U.S. Patent Document 2005/239976 describes polymers that are similar to the present polymers but do not have a reverse comonomer distribution.

Summary of the invention

This summary is provided to introduce a selection of concepts in a simplified manner, which are described below in the detailed description. This summary is not intended to identify the required or essential characteristics of the claimed object. Nor is it intended that this summary limit the scope of the claimed object.

According to the invention, an olefin polymer is provided as defined in the attached claim 1.

New catalytic compositions, methods for preparing catalytic compositions, methods for using catalytic compositions to polymerize olefins, polymeric resins produced using said catalytic compositions, and articles produced using these polymeric resins are described herein. In particular, aspects of the present invention relate to catalytic compositions employing three metallocene catalyst components. The first catalytic component may comprise a metallocene compound based on zirconium or hafnium without bridges and / or a dinuclear metallocene compound based on zirconium and / or hafnium without bridges; the second catalytic component may comprise a zirconium-based metallocene compound with bridges with a fluorenyl group and without aryl groups in the bridging group and the third catalytic component may comprise a zirconium or hafnium-based metallocene compound with bridges with a fluorenyl group and an aryl group in the bridge forming group. Such catalytic compositions can be used to produce, for example, ethylene-based homopolymers and copolymers with wide molecular weight distributions.

A catalytic composition that can comprise the first metallocene catalyst component, the second metallocene catalyst component, the third metallocene component and an activator is also described. Optionally, this catalytic composition may further comprise a cocatalyst.

In addition, olefin polymerization processes are described. Such processes may comprise contacting a catalytic composition with an olefin monomer and, optionally, an olefin comonomer under polymerization conditions to produce an olefinic polymer. Generally, the catalyst composition employed may comprise any of the metallocene compounds of catalyst component I, any of the metallocene compounds of catalyst component II, any of the metallocene compounds of catalyst component III and any of the optional activators and cocatalysts described in The present memory. For example, organoaluminum compounds can be used in catalytic compositions and / or in polymerization processes.

The polymers produced from the polymerization of olefins, which results in homopolymers, copolymers, terpolymers, etc., can be used to produce various articles of manufacture.

Both the above summary and the following detailed description provide examples and are only explanatory. Therefore, the previous summary and the following detailed description should not be considered as restrictive. In addition, features or variations may be provided in addition to those set forth herein. For example, some aspects and embodiments can be directed to different combinations and sub-combinations of features described in the detailed description.

Brief description of the figures

Figure 1 illustrates a representative bimodal molecular weight distribution curve.

Figure 2 illustrates a representative bimodal molecular weight distribution curve.

Figure 3 illustrates a representative bimodal molecular weight distribution curve.

Figure 4 illustrates a representative bimodal molecular weight distribution curve.

Figure 5 illustrates a representative bimodal molecular weight distribution curve.

Figure 6 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 7 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 8 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 9 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 10 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 11 illustrates a representative non-bimodal molecular weight distribution curve.

Figure 12 illustrates the definitions of D85 and D15 in a molecular weight distribution curve.

Figure 13 illustrates the definitions of D50 and D10 in a molecular weight distribution curve and the short chain branching content in D50 and D10.

Figure 14 presents a graph of the molecular weight distributions of the polymers of Examples 1-6. Figure 15 presents a graph of the short chain branching distribution of the polymer of Example 1. Figure 16 shows a graph of the short chain branching distribution of the polymer of Example 2. Figure 17 presents a graph of the distribution of polymer Short chain branching of the polymer of Example 3. Figure 18 shows a graph of the short chain branching distribution of the polymer of Example 4. Figure 19 shows a graph of the short chain branching distribution of the polymers of the examples 5-6.

Definitions

To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this description. If a term is used in this description, but is not specifically defined herein, the definition of IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997) may be applied, provided that such definition does not contradict any other description or definition applied herein, or make any claim to which said definition applies indefinite or not allowed.

Taking into account the terms or expressions of transition of the claims, the transition term "comprising", which is synonymous with "including", "containing" or "characterized by", is open and does not exclude elements not mentioned or steps of the method, additional. The transition term "consisting of" excludes any element, stage or ingredient not specified in the claim. The term "essentially consisting of" transitions limits the scope of a claim to the specified components or stages and to those that do not materially affect the basic (s) and novel feature (s) of the invention. claimed. A claim "consisting essentially of" represents a medium degree between closed claims that are written in a "consisting of" format and fully open claims that are written in a "comprising" format. For example, a raw material consisting essentially of component A may include impurities typically present in a commercially produced or commercially available sample of component A. When a claim includes different features and / or kinds of features (for example, a method step, traits of the raw material and / or traits of the product, among other possibilities), the transition terms that it comprises, consisting essentially of, and consisting of, apply only to the kind of feature for which they are used and is possible that different transition terms or expressions with different features be used in a claim. For example, a method may consist of certain steps, but a catalytic system comprising cited components and other uncited components is used. Although compositions and methods are described in the present invention in terms of "comprising" various components or stages, the compositions and methods may also "essentially consist of" or "consist of" the various components or stages, unless indicated otherwise. For example, a catalytic composition consistent with aspects of the present invention may comprise; alternatively, it may consist essentially of; or alternatively, it may consist of; (i) a catalytic component I, (ii) a catalytic component II, (iii) an activator and (iv) optionally, a cocatalyst.

Element groups are indicated by the use of the numbering scheme indicated in the version of the periodic table of the elements published in Chemical and Engineering News, 63 (5), 27, 1985. In some cases, a group of elements using a common name assigned to the group; for example, alkali metals for elements of group 1, alkaline earth metals for elements of group 2, transition metals for elements of groups 3-12 and halogens or halides for elements of group 17.

It is also intended that, for any particular compound described herein, the name or general structure presented encompasses all structural isomers, conformation isomers and stereoisomers that may be raised from a particular set of substituents, unless indicate otherwise. Thus, a general reference to a compound includes all structural isomers, unless explicitly stated otherwise; for example, a general reference to pentane includes: n-pentane, 2-methylbutane and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group. Additionally, the reference to a general name or structure encompasses all enantiomers, diastereomers and other optical isomers in enantiomeric or racemic forms, as well as mixtures of stereoisomers, to the extent permitted or required by the context. For any particular name or formula presented, any general name or formula presented also encompasses all conformational isomers, regioisomers and stereoisomers that may be raised from a particular set of substituents.

A chemical "group" is described according to how that group is formally derived from a reference compound or "precursor", for example, by the number of hydrogen atoms that are formally removed from the precursor compound to generate the group, even if that group does not It is literally synthesized in this way. These groups can be used as substituents or coordinate or bind to metal atoms. As an example, an "alkyl group" can be formally derived by removing a hydrogen atom from an alkane, while an "alkylene group" can be formally derived by removing two hydrogen atoms from an alkane. In addition, a more general term can be used to encompass a variety of groups that formally derive from the removal of any number ("one or more") of hydrogen atoms from a precursor compound, which in this example can be described as a "alkane group "And encompassing an" alkyl group, "an" alkylene group, "and materials in which three or more hydrogen atoms have been removed, as necessary for the situation, from the alkane. The description that a substituent, a ligand or other chemical moiety may constitute a particular "group" implies that the known rules of chemical structure and bond are followed when that group is employed as described. When it is described that a group "drifts by", "drifts by", "is formed by" or "is formed by", these terms are used in a formal sense and are not intended to reflect any specific synthetic method or procedure, to unless otherwise specified or context requires otherwise.

The term "substituted", when used to describe a group, for example, when referring to a substituted analog of a particular group, describes any non-hydrogen residue that formally replaces a hydrogen in that group and is not intended to be limiting A group or groups may also be referred to herein as "unsubstituted (s)" or with equivalent terms such as "unsubstituted", which refer to the original group in which the non-hydrogen moiety does not replace a hydrogen within that group. Unless otherwise specified, it is intended that "substituted" is not limiting and includes inorganic substituents or organic substituents, as understood by one skilled in the art.

The term "hydrocarbon", whenever used herein and in the claims, refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of particular groups in the hydrocarbon (for example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms to replace an equivalent number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl group" is used herein according to the definition specified by the IUPAC: a univalent group formed by the removal of a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl and the like. Similarly, a "hydrocarbylene group" refers to a group formed by the removal of two hydrogen atoms from a hydrocarbon, either two hydrogen atoms from a carbon atom or a hydrogen atom from each of two carbon atoms different. Therefore, according to the terminology used herein, a "hydrocarbon group" refers to a generalized group formed by the removal of one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon. A "hydrocarbyl group", a "hydrocarbylene group" and a "hydrocarbon group" can be aliphatic or aromatic, acyclic or cyclic and / or linear or branched groups. A "hydrocarbyl group", a "hydrocarbylene group" and a "hydrocarbon group" may include rings, ring systems, aromatic rings and aromatic ring systems, containing only carbon and hydrogen. The "hydrocarbyl groups", the "hydrocarbylene groups" and the "hydrocarbon groups" include, for example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene and aralkane groups, respectively, among other groups as members.

An aliphatic compound is a class of cyclic or acyclic carbon compound, saturated or unsaturated, excluding aromatic compounds, for example, an aliphatic compound is a non-aromatic organic compound. An "aliphatic group" is a generalized group formed by the removal of one or more hydrogen atoms (as necessary for the particular group) from a carbon atom of an aliphatic compound. The aliphatic compounds and, therefore, the aliphatic groups may contain an organic functional group (s) and / or a different atom (s) of carbon and hydrogen.

The term "alkane", whenever used herein and in the claims, refers to a saturated hydrocarbon compound. Other identifiers can be used to indicate the presence of particular groups in the alkane (for example, halogenated alkane indicates the presence of one or more halogen atoms to replace an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used herein according to the definition specified by the IUPAC: a univalent group formed by the removal of a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by the removal of two hydrogen atoms from an alkane (either two hydrogen atoms from a carbon atom or a hydrogen atom from two different carbon atoms). An "alkane group" is a general term that refers to a group formed by the removal of one or more hydrogen atoms (as necessary for the particular group) from an alkane. An "alkyl group", an "alkylene group" and an "alkane group" may be acyclic or cyclic and / or linear or branched groups, unless otherwise specified. The primary, secondary and tertiary alkyl groups derive from the removal of a hydrogen atom from a primary, secondary and tertiary carbon atom, respectively, of an alkane. The n-alkyl group can be derived from the removal of a hydrogen atom from a terminal carbon atom from a linear alkane. The RCH2 (R # H), R2CH (R # H) and R3C (R # H) groups are primary, secondary and tertiary alkyl groups, respectively.

A cycloalkane is a saturated cyclic hydrocarbon, with or without side chains, for example, cyclobutane. Other identifiers can be used to indicate the presence of particular groups in the cycloalkane (for example, halogenated cycloalkane indicates the presence of one or more halogen atoms to replace an equivalent number of hydrogen atoms in the cycloalkane). Unsaturated cyclic hydrocarbons having a double bond or an endocyclic triple bond are called cycloalkenes and cycloalkynes, respectively. Those with more than one multiple bond are cycloalkanes, cycloalkatriennes, etc. Other identifiers can be used to indicate the presence of particular groups in cycloalkenes, cycloalcadienos, cycloalcatrienos, etc.

A "cycloalkyl group" is a univalent group derived from the removal of a hydrogen atom from a carbon atom from the ring of a cycloalkane. For example, a 1-methylcyclopropyl group and a 2-methylcyclopropyl group are illustrated as follows.

Similarly, a "cycloalkylene group" refers to a group derived from the removal of two hydrogen atoms from a cycloalkane, at least one of which is a ring carbon. Thus, a "cycloalkylene group" includes a group derived from a cycloalkane in which two hydrogen atoms are formally removed from the same carbon of the ring, a group derived from a cycloalkane in which two hydrogen atoms are formally removed from two carbons of Different ring and a group derived from a cycloalkane in which a first hydrogen atom is formally removed from a carbon in the ring and a second hydrogen atom is formally removed from a carbon atom that is not a ring carbon. A "cycloalkane group" refers to a generalized group formed by the removal of one or more hydrogen atoms (as necessary for the particular group and at least one of which is a ring carbon) from a cycloalkane.

The term "alkene" provided that it is used herein and in the claims refers to a linear or branched hybridized olefin having a carbon-carbon double bond and the general formula CnH2n. Alkanes refers to a linear or branched hydrocarbon olefin having two carbon-carbon double bonds and the general formula CnH2n-2 and alkaliennes refers to linear or branched hybridized olefins having three carbon-carbon bonds and the general formula CnH2n-4. Alkenes, alcadienos and alcatrienos can also be identified by the position of the carbon-carbon double bonds. Other identifiers may be used to indicate the presence or absence of particular groups in an alkene, an alkane or an alkaliene. For example, a haloalkene refers to an alkene that has one or more hydrogen atoms to replace with a halogen atom.

An "alkenyl group" is a univalent group derived from an alkene by the removal of a hydrogen atom from any carbon atom of the alkene. Thus, "alkenyl group" includes groups in which hydrogen atoms are formally removed from a sp2 hybridized (olefinic) carbon atom and groups in which the hydrogen atom is formally removed from any other carbon atom. For example, unless otherwise specified, the 1-propenyl (-CH = CHCH3), 2-propenyl (-CH2CH = CH2) and 3-butenyl (-CH2CH2CH = CH2) groups are encompassed in the term "alkenyl group ». Similarly, an "alkenylene group" refers to a group formed by the formal removal of two hydrogen atoms from an alkene, either two hydrogen atoms from a carbon atom or a hydrogen atom from each of two atoms of different carbon. An "alkene group" refers to a generalized group formed by the removal of one or more hydrogen atoms (as necessary for the group particular) of an alkene. When the hydrogen atom is removed from a carbon atom that participates in a carbon-carbon double bond, the carbon regiochemistry from which the hydrogen atom is removed and the carbon-carbon double bond regiochemistry can be specified. Other identifiers can be used to indicate the presence or absence of particular groups in an alkene group. Alkene groups can also be identified by the position of the carbon-carbon double bond.

A sand is an aromatic hydrocarbon, with or without side chains (for example, benzene, toluene or xylene, among others). The "aryl group" is a group derived from the formal removal of a hydrogen atom from a carbon atom from the aromatic ring of a sand. It should be noted that the sand may contain a single aromatic hydrocarbon ring (e.g., benzene or toluene), contain condensed aromatic rings (e.g., naphthalene or anthracene) and contain one or more isolated aromatic rings linked by covalent bonds by a bond ( for example, biphenyl) or non-aromatic hydrocarbon groups (for example, diphenylmethane). An example of an "aryl group" is orfo-tolyl (o-tolyl), whose structure is shown here.

An "aralkyl group" is an arylsubstituted alkyl group having a free valence in a non-aromatic carbon atom, for example, a benzyl group, or a 2-phenyle-1-yl group, among others.

A "halide" has its usual meaning. Examples of halides include fluoride, chloride, bromide and iodide.

The term "polymer" is used herein generically to include homopolymers, copolymers, terpolymers, etc. A copolymer is derived from an olefinic monomer and an olefinic comonomer, while a terpolymer is derived from an olefinic monomer and two olefinic comonomers. Accordingly, "polymer" encompasses copolymers, terpolymers, etc. derivatives of any olefinic monomer and comonomer (s) described herein. Similarly, an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers and the like. As an example, an olefinic copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene or 1-cytene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer could be categorized as an ethylene / 1-hexene copolymer.

Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process may involve the contact of an olefinic monomer (for example, ethylene) and an olefinic comonomer (for example, 1-hexene) to produce a copolymer.

The term "cocatalyst" is generally used herein to refer to compounds such as aluminoxane compounds, organoboro or organoborate compounds, ionizing ionic compounds, organoaluminium compounds, organocinc compounds, organomagnesium compounds, organolithium compounds and the like, which may constitute a component of a catalytic composition, when used, for example, in addition to an activating support. The term "cocatalyst" is used without regard to the actual function of the compound or any chemical mechanism by which the compound can operate.

The terms "chemically treated solid oxide", "treated solid oxide compound" and the like, are used herein to indicate a relatively high porosity solid inorganic oxide, which may exhibit Lewis acid or Bransted acid behavior and that has been treated with an electron acceptor component, typically an anion, and that is calcined. The electron acceptor component is typically an electron acceptor anion source compound. Thus, the chemically treated solid oxide may comprise a calcined contact product of at least one solid oxide with at least one electron acceptor anion source compound. Typically, the chemically treated solid oxide comprises at least one acidic solid oxide compound. The "activating support" of the present invention may be a chemically treated solid oxide. The terms "support" and "activating support" do not imply that these components are inert and it should not be construed that these components are inert components of the catalytic composition. The term "activator," as used herein, generally refers to a substance that can convert a metallocene component into a catalyst that can polymerize olefins or convert a contact product of a metallocene component and a component that provides an activatable ligand (for example, an alkyl, a hydride) to the metallocene, when the metallocene compound does not already comprise said ligand, in a catalyst that can polymerize olefins. This term is used regardless of the actual activation mechanism. Illustrative activators include activator supports, aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds and the like. Aluminoxanes, organoboro or organoborate compounds and ionizing ionic compounds are generally referred to as activators if they are used in a catalytic composition in which there is no activating support. If the catalytic composition contains an activating support, then aluminoxane, organoboro or organoborate materials and ionizing ionic materials are typically referred to as cocatalysts.

The term "fluoroorganoboro compound" is used herein with its ordinary meaning to refer to neutral compounds of the form BY3. The term "fluoroorganoborate compound" also has its meaning usual to refer to the monoanionic salts of a fluoroorganoboro compound of the form [cation] + [BY4] -, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboro or organoborate compounds".

The terms "metallocene", "metallocene without a bridge" and "metallocene with bridges", as used herein, describe compounds comprising at least one ^ 5-cycloalcadienyl type moiety, wherein moieties at ^ 5- Cycloalcadienyl include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands and the like, including analogs or partially saturated or substituted derivatives of any of these. Possible substituents in these ligands may include H, therefore, this invention comprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated saturated indenyl, partially saturated saturated fluorenyl and the like. In some contexts, metallocene can be referred to simply as a "catalyst", in the same way that the term "cocatalyst" can be used herein to refer, for example, to an organoaluminum compound.

The terms "catalytic composition", "catalytic mixture", "catalytic system", and the like, do not depend on the actual product or composition resulting from the contact or reaction of the initial components of the claimed catalyst composition / mixture / system, of the nature of the active catalytic site or of the destination of the cocatalyst, of the metallocene compounds, of any olefinic monomer used to prepare a mixture with which it has been previously contacted, or of the activator (for example, activator support), after Combine these components. Therefore, the terms "catalytic composition", "catalytic mixture", "catalytic system", and the like, encompass the initial starting components of the composition, as well as any products that may result from the contact of these initial starting components and This includes both homogeneous and heterogeneous catalyst compositions or systems. The terms "catalytic composition", "catalytic mixture", "catalytic system", and the like, are used interchangeably throughout the present description.

The term "contact product" is used herein to describe compositions where the components are contacted in any order, in any form and for any period of time. For example, the components can be contacted by mixing or mixing. In addition, contact of any component may occur in the presence or absence of any other component of the compositions described herein. Additional components or materials can be combined by any suitable method. In addition, the term "contact product" includes mixtures, mixtures, solutions, suspensions, reaction products and the like, or combinations thereof. Although "contact product" may include reaction products, the respective components are not required to react with each other. Similarly, the term "contact" is used herein to refer to materials that can be mixed, mixed, suspended, dissolved, reacted, treated, or otherwise contacted in some other way.

The term "previously contacted" mixture is used herein to describe a first mixture of catalytic components that come into contact for a first period of time prior to the first mixture being used to form a "contact" mixture. subsequently »or second mixture of catalytic components that come into contact for a second period of time. Typically, the previously contacted mixture may describe a mixture of a metallocene compound (one or more than one), olefin monomer (or monomers), and organoaluminum compound (or compounds), before this mixture is placed in contact with a support or activating supports and optional additional organoaluminum compound. Thus, previously contacted describes components that are used to contact each other, but prior to contacting the components in the second mixture, subsequently contacted. Accordingly, this invention can occasionally distinguish between a component used to prepare the previously contacted mixture and that component after the mixture has been prepared. For example, according to this description, it is possible that the organoaluminum compound previously contacted, once it is contacted with the metallocene compound and the olefinic monomer, reacts to form at least one compound, formulation or chemical structure different from the different organoaluminum compound used to prepare the previously contacted mixture. In this case, the previously contacted organoaluminum compound or component is described as comprising an organoaluminum compound that was used to prepare the previously contacted mixture.

Additionally, the previously contacted mixture may describe a mixture of metallocene compound (s) and organoaluminum compound (s), before this mixture is contacted with one or more activating supports. This previously contacted mixture may also describe a mixture of metallocene compound (s), olefinic monomer (s) and activator support (s), before this mixture is contacted with a cocatalyst compound or compounds of organoaluminum

Similarly, the term "subsequently contacted" mixture is used herein to describe a second mixture of catalytic components that come into contact for a second period of time and a constituent of which is the "put into contact" mixture. pre-contact »or first mixture of the catalytic components that were contacted for a first period of time. Typically, the term "subsequent contact" mixture is used herein to describe the mixture of metallocene compound (s), olefinic monomer (s), organoaluminum compound (s) and activator support (s) (is) trained to from the contacting of the previously contacted mixture of a portion of these components with any additional component added to constitute the subsequently contacted mixture. Frequently, the activating support may comprise a chemically treated solid oxide. For example, the additional component added to constitute the subsequently contacted mixture may be a chemically treated solid oxide (one or more than one), and optionally, it may include an organoaluminum compound that is the same as the organoaluminum compound, or other than it, used to prepare the previously contacted mixture, as described herein. Accordingly, this invention may occasionally distinguish between a component used to prepare the subsequently contacted mixture and that component after the mixture has been prepared.

Although any methods, devices and materials similar or equivalent to those described herein can be used to carry out or evaluate the invention, typical methods, devices and materials are described herein.

Detailed description of the invention

The present invention is directed generally to new olefin polymers and articles produced using these polymers. Catalytic compositions containing three metallocene components and polymerization processes using said catalytic compositions are also described herein.

Catalytic Component I

The catalytic component I may comprise a hafnium or zirconium-based metallocene compound without bridges and / or a dinuclear metallocene compound based on zirconium and / or bridges without hafnium. In one aspect, for example, the catalyst component I may comprise a hafnium or zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups or an indenyl group and a cyclopentadienyl group. In another aspect, the catalytic component I may comprise a zirconium-based metallocene compound without bridges containing two cyclopentadienyl groups, two indenyl groups or an indenyl group and a cyclopentadienyl group. In yet another aspect of this invention, the catalytic component I may comprise a metallocene compound without bridges of formula ( A ):

In formula ( A ), M1, CpA, CpB and each X are independent elements of the metallocene compound without bridges. Accordingly, the metallocene compound without bridges of formula ( A ) can be described using any combination of M1, CpA, CpB and X described herein.

Unless otherwise specified, formula ( A ) above, any other structural formulas described herein and any complex, compound or species of metallocene described herein are not designed to show the stereochemistry or isomeric location of the different moieties (for example, these formulas are not intended to exhibit cis or trans isomers, or R or S diastereomers), although said formulas and / or structures contemplate and encompass said compounds.

According to aspects of this invention, the metal in the formula ( A ), M1, can be Zr or Hf. In one aspect, for example, M1 can be Zr, while in another aspect, M1 can be Hf.

Each X in the formula ( A ) can independently be a monoanionic ligand. In some aspects, suitable monoanionic ligands may include H (hydride), BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylamino group, a C1 to C36 hydrocarbylsilyl group, a group C1 to C36 hydrocarbylaminylsilyl, -OBR12 or -OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group, but not limited to these. It is contemplated that each X may be the same monoanionic ligand or a different one.

In one aspect, each X can independently be H, BH4, a halide (for example, F, Cl, Br, etc.), a C1 to C18 hydrocarbyl group, a C1 to C18 hydrocarboxy group, a C1 to C18 hydrocarbylamino group, a C ¹ to C ¹⁸ hydrocarbylsilyl group or a C ¹ to C ¹⁸ hydrocarbylaminylsilyl group. Alternatively, each X can independently be H, BH ⁴ , a halide, OBR ¹² or OSO ² R ¹ , wherein R ¹ is a C ¹ to C ¹⁸ hydrocarbyl group. In another aspect, each X can independently be H, BH ⁴ , a halide, a C ¹ to C ¹² hydrocarbyl group, a C ¹ to C ¹² hydrocarboxy group, a C ¹ to C ¹² hydrocarbylamino group, a C ¹ to hydrocarbylsilyl group C12, a C ¹ to C ¹² hydrocarbylaminylsilyl group, OBR ¹² or OSO ² R ¹ , wherein R ¹ is a C ¹ to C ¹² hydrocarbyl group. In another aspect, each X may independently be H, BH4, a halide, a C1 to C10 hydrocarbyl group, a C1 to C10 hydrocarboxy group, a C1 to C10 hydrocarbylamino group, a C1 to C10 hydrocarbylsilyl group, a C1 to C10 hydrocarbylamino group , OBR12 or OSO2R1, where R ¹ is a C1 to C10 hydrocarbyl group. In yet another aspect, each X can independently be H, BH4, a halide, a C1 to C ⁸ hydrocarbyl group, a C1 to C ⁸ hydrocarboxy group, a C1 to C ⁸ hydrocarbylamino group, a C1 to hydrocarbylsilyl group C ⁸ , a C ⁸ to C ⁸ , OBR12 or OSO ² R ¹ hydrocarbylaminylsilyl group, wherein R ¹ is a C 1 to C ⁸ hydrocarbyl group. In even another aspect, each X can independently be a halide or a hydrocarbyl group Ci to Ci ⁸ . For example, X can be Cl.

The hydrocarbyl group which may be an X in the formula ( A ) may be a C1 to C36 hydrocarbyl group, including a C1 to C36 alkyl group, a C2 to C36 alkenyl group, a C4 to C36 cycloalkyl group, a C ⁶ aryl group to C36 or a C7 to C36 aralkyl group, but not limited to these. For example, each X may be independently a C1 to C18 group, an alkenyl group C2 to C18, cycloalkyl group C4 to C18, an aryl group C ⁶ to C18 aralkyl group or C7 to C18; alternatively, each X may be independently a C1 to C12 alkyl group, an alkenyl group C2 to C12 cycloalkyl group C4 to C12, an aryl group C ⁶ to C12 aralkyl group or C7 to C12; alternatively, each X may be independently a C1 to C10 alkyl group, an alkenyl group C2 to C10, cycloalkyl group C4 to C10, an aryl group C ⁶ to C10 aralkyl group or C7 to C10; or alternatively, each X may independently be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C ⁸ cycloalkyl group, a C ⁶ to C ⁸ aryl group or a C7 to C ⁸ aralkyl group.

Accordingly, in some aspects, the alkyl group which may be an X in the formula ( A ) may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group or alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group. In some aspects, the alkyl group which may be an X in the formula ( A ) may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a group sec-butyl, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group or a neopentyl group; alternatively, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a neopentyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group; alternatively, an isopropyl group; alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups that may be an X in the formula ( A ) may include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a Decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group or an octadecenyl group, but not limited to these. Such alkenyl groups can be linear or branched and the double bond can be located anywhere in the chain. In one aspect, each X in the formula ( A ) can independently be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group or a decenyl group , while in another aspect, each X in the formula ( A ) can independently be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group or a hexenyl group. For example, an X may be an ethenyl group; alternatively, a propenyl group; alternatively, a butenyl group; alternatively, a pentenyl group; or alternatively, a hexenyl group. In even another aspect, an X may be a terminal alkenyl group, such as a C3 to C18 terminal alkenyl group, a C3 to C12 terminal alkenyl group or a C3 to C ⁸ terminal alkenyl group. Illustrative terminal alkenyl groups may include a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-yl group, a hex-5-en- group 1-yl, a hept-6-en-1-yl group, an octe-7-en-1-yl group, a non-8-en-1-yl group, a dece-9-en-1- group ilo, etc., not limited to these.

Each X in the formula ( A ) can be a cycloalkyl group, including a cyclobutyl group, a substituted cyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group , a cyclooctyl group or a substituted cyclooctyl group, but not limited to these. For example, an X in the formula ( A ) can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group or a substituted cyclohexyl group. In addition, each X in the formula ( A ) can independently be a cyclobutyl group or a substituted cyclobutyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cycloheptyl group or a substituted cycloheptyl group; alternatively, a cyclooctyl group or a substituted cyclooctyl group; alternatively, a cyclopentyl group; alternatively, a substituted cyclopentyl group; alternatively, a cyclohexyl group; or alternatively, a substituted cyclohexyl group. Substituents that can be used for the substituted cycloalkyl group are independently described herein and can be used without limitation to further describe the substituted cycloalkyl group which may be an X in the formula ( A ).

In some aspects, the aryl group which may be an X in the formula ( A ) may be a phenyl group, a substituted phenyl group, a naphthyl group or a substituted naphthyl group. In one aspect, the aryl group may be a phenyl group or a substituted phenyl group; alternatively, a naphthyl group or a substituted naphthyl group; alternatively, a phenyl group or a naphthyl group; alternatively, a substituted phenyl group or a substituted naphthyl group; alternatively, a phenyl group; or alternatively, a naphthyl group. Substituents that can be used for substituted phenyl groups or substituted naphthyl groups are independently described herein and can be used without limitation to further describe substituted phenyl groups or substituted naphthyl groups that may be an X in the formula. ( A )

In one aspect, the substituted phenyl group which may be an X in the formula ( A ) may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2.4-substituted phenyl group , a phenyl group disubstituted in 2.6, a phenyl group disubstituted in 3.5 or a phenyl group trisubstituted in 2.4.6. In other aspects, the substituted phenyl group may be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2.4-substituted phenyl group or a 2.6-substituted phenyl group; alternatively, a phenyl group substituted at 3 or a phenyl group substituted at 3.5; alternatively, a phenyl group substituted in 2 or a phenyl group substituted in 4; alternatively, a phenyl group disubstituted in 2.4 or a phenyl group disubstituted in 2.6; alternatively, a phenyl group substituted at 2; alternatively, a phenyl group substituted at 3; alternatively, a phenyl group substituted at 4; alternatively, a phenyl group disubstituted in 2.4; alternatively, a phenyl group disubstituted in 2.6; alternatively, a phenyl group disubstituted in 3.5; or alternatively, a phenyl group trisubstituted in 2,4,6. Substituents that can be used for these specific substituted phenyl groups are independently described herein and can be used, without limitation, to further describe these substituted phenyl groups which may be one or more X groups in the formula ( A ).

In some aspects, the aralkyl group which can be an X group in the formula ( A ) can be a benzyl group or a substituted benzyl group. In one aspect, the aralkyl group may be a benzyl group or, alternatively, a substituted benzyl group. Substituents that can be used for the substituted aralkyl group are independently described herein and can be used, without limitation, to further describe the substituted aralkyl group which may be one or more X groups in the formula ( A ).

In one aspect, each different hydrogen substituent for the substituted cycloalkyl group, the substituted aryl group or the substituted aralkyl group which may be an X in the formula ( A ) can independently be a C1 to C18 hydrocarbyl group; alternatively, a C1 to C8 hydrocarbyl group or, alternatively, a C1 to C5 hydrocarbyl group. Specific hydrocarbyl groups are independently described herein and can be used, without limitation, to further describe the substituents of the substituted cycloalkyl groups, the substituted aryl groups or the substituted aralkyl groups which may be an X in the formula ( A ). For example, the hydrocarbyl substituent may be an alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a group tert-butyl, an n-pentyl group, a 2- pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a 3-methyl-1-butyl group, a group 3- methyl-2-butyl or a neo-pentyl group, and the like. Also, the hydrocarbyl substituent may be a benzyl group, a phenyl group, a tolyl group or an xylyl group, and the like.

A hydrocarboxy group is used generically herein to include, for example, alkoxy, aryloxy, aralkoxy, - (alkyl, aryl or aralkyl) -O- (alkyl, aryl or aralkyl) and -O (CO) groups - hydrogen or hydrocarbyl), and these groups may comprise up to about 36 carbon atoms (for example, hydrocarboxy groups of C1 to C36, C1 to C18, C1 to C10 or C1 to C8). Non-limiting illustrative examples of hydrocarboxy groups that may be an X in the formula ( A ) may include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl group 1-Butoxy, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group, a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, a benzoxy group, an acetylacetonate group ( acac), a formate group, an acetate group, a stearate group, an oleate group, a benzoate group and the like, but not limited to these. In one aspect, the hydrocarboxy group which can be an X in the formula ( A ) can be a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an isopropoxy group; alternatively, an n-butoxy group; alternatively, a sec-butoxy group; alternatively, an isobutoxy group; alternatively, a tert-butoxy group; alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group; alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxy group; alternatively, a tert-pentoxy group; alternatively, a 3-methyl-1-butoxy group; alternatively, a 3-methyl-2-butoxy group; alternatively, a neo-pentoxy group; alternatively, a phenoxy group; alternatively, a toloxy group; alternatively, a xyloxy group; alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxy group; alternatively, an acetylacetonate group; alternatively, a formate group; alternatively, an acetate group; alternatively, a stearate group; alternatively, an oleate group; or alternatively, a benzoate group.

The term "hydrocarbylaminyl group" is used to refer generically herein collectively, for example, to alkylaminyl, arylaminyl, aralkylaminyl, dialkylamino, diarylaminyl, diaralkylamino and - (alkyl, aryl or aralkyl) -N- (alkyl, aryl) groups. or aralkyl), and, unless otherwise specified, hydrocarbylaminyl groups which may be X in formula ( A ) may comprise up to about 36 carbon atoms (eg, hydrocarbylamino groups of C1 to C36, C1 to C18, C1 to C10 or C1 to C8). Accordingly, it is intended that the hydrocarbylaminyl cover both (mono) hydrocarbylaminyl and dihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl group which may be an X in the formula ( A ) may be, for example, a methylaminyl group (-NHCH3), an ethylaminyl group (-NHCH2CH3), an n-propylamino group (-NHCH2CH2CH3), an isopropylaminyl group (-NHCH (CH3) 2), an n-butylaminyl group (-NHCH2CH2CH2CH3), a t-butylaminyl group (-NHC (CH3) 3), an n-pentylamino group (-NHCH2CH2CH2CH2CH3), a neo- pentylaminyl (-NHCH2C (CH3) 3), a phenylaminyl group (-NHC6H5), a tolylaminyl group (-NHC6H4CH3) or a xylaminyl group (-NHC6H3 (CH3) 2); alternatively, a methylaminyl group; alternatively, an ethylamino group; alternatively, a propylamino group; or alternatively, a phenylamino group. In other aspects, the hydrocarbylaminyl group which can be an X in the formula ( A ) can be, for example, a dimethylaminyl group (-N (CH3) 2), a diethylaminyl group (-N (CH2CH3) 2), a group di-n-propylaminyl (-N (CH2CH2CH3) 2), a di-isopropylaminyl group (-N (CH (Ch 3) 2) 2), an n-butylaminyl group (-N (c H2CH2c H2CH3) 2), a di-t-butylaminyl group (-N (C (CH3) 3) 2), a di-n-pentylaminyl group (-N (CH2CH2CH2CH2CH3) 2), a di-neopentylaminyl group (-N (CH2C (CH3) 3)) 2), a diphenylaminyl group (-N (C6H5) 2), a ditolylamino group (-N (C6H4CH3) 2) or a dixylaminyl group (-N (C6H3 (CH3) 2) 2); alternatively, a dimethylaminyl group; alternatively, a diethylaminyl group; alternatively, a di-n-propylaminyl group; or alternatively, a diphenylaminyl group.

According to some aspects described herein, each X can independently be a C1 to C36 hydrocarbylsilyl group; alternatively, a C1 to C24 hydrocarbylsilyl group; a C1 to C18 hydrocarbylsilyl group; or alternatively a C1 to C ⁸ hydrocarbylsilyl group. In one aspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group may be any hydrocarbyl group described herein (e.g., an alkyl group C1 to C5, an alkenyl group C2 to C5, a cycloalkyl group C5 to ^C8 a C ⁶ aryl group to C ^8, an aralkyl group C7 to C ^8, etc.). As used herein, it is intended that hydrocarbylsilyl cover (mono) hydrocarbylsilyl (-SH 2R), dihydrocarbylsilyl (-SHR2) and trihydrocarbylsilyl (-SiR3) groups, wherein R is a hydrocarbyl group. In one aspect, the hydrocarbylsilyl group may be a C3 to C36 or C3 to C18 trihydrocarbylsilyl group, such as, for example, a trialkylsilyl group or a triphenylsilyl group. Non-limiting illustrative examples of hydrocarbylsilyl groups which may be X groups in the formula ( A ) may include trimethylsilyl, triethylsilyl, tripropylsilyl (for example, triisopropylsilyl), tributyl silyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl and the like, but not limited thereto.

A hydrocarbylaminylsilyl group is used herein to refer to groups containing at least one hydrocarbon moiety, at least one N atom and at least one Si atom. Non-limiting illustrative examples of hydrocarbylaminylsilyl groups that may be an X may include -N (SiMe3) 2, -N (SiEt3) 2 and the like, but not limited to these. Unless otherwise specified, hydrocarbylaminylsilyl groups that may be X may comprise up to about 36 carbon atoms (for example, hydrocarbylaminylsilyl groups of C1 to C36, C1 to C18, C1 to C12 or C1 to C ⁸ ). In one aspect, each hydrocarbyl (one or more) of the hydrocarbylaminylsilyl group may be any hydrocarbyl group described herein (for example, a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C ⁸ cycloalkyl group a C ⁶ aryl group to C ^8, an aralkyl group C7 to C ^8, etc.). In addition, it is intended that hydrocarbylaminylsilyl cover groups -NH (SiH2R), -NH (SiHR2), -NH (SiR3), -N (SiH2R) 2, -N (SiHR2) 2 and -N (SiR3) 2 among others, being R a hydrocarbyl group.

In one aspect, each X can independently be -OBR12 or -OSO2R1, wherein R ¹ is a C1 to C36 hydrocarbyl group, or alternatively, a C1 to C18 hydrocarbyl group. The hydrocarbyl group at OBR12 and / or OSO2R1 can independently be any hydrocarbyl group described herein, such as, for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, a group C ⁶ to C ¹⁸ aryl or a C ⁷ to C 18 aralkyl group; alternatively a C1 to C12 alkyl group, an alkenyl group C2 to C12 cycloalkyl group C4 to C12, a C ⁶ to C12 aryl group or an aralkyl group C7 through C12; or alternatively, a C1 to C ⁸ alkyl group, a C2 to C ⁸ alkenyl group, a C5 to C ⁸ cycloalkyl group, a C ⁶ to C ⁸ aryl group or a C7 to C ⁸ aralkyl group.

In one aspect, each X may independently be H, BH4, a halide or a C1 to C36 hydrocarbyl group, a hydrocarboxy group, a hydrocarbylaminyl group, a hydrocarbylsilyl group or a hydrocarbylaminylsilyl group, while in another aspect, each X may independently be H , BH4, or a C1 to C18 hydrocarboxy group, a hydrocarbylaminyl group, a hydrocarbylsilyl group, or a hydrocarbylaminylsilyl group. In yet another aspect, each X can independently be a halide; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylaminyl group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylaminylsilyl group. In another aspect, each X can be H; alternatively, F; alternatively, Cl; alternatively, Br; alternatively, I; alternatively BEL4; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylaminyl group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylaminylsilyl group.

Each X may independently be, in some aspects, H, a halide, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate, acetate, stearate, oleate, benzoate, an alkylamino, a dialkylamino, a trihydrocarbylsilyl or a hydrocarbylaminylsilyl ; alternatively, H, a halide, methyl, phenyl or benzyl; alternatively, an alkoxy, an aryloxy or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl; alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl; alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl or a dialkylamino; alternatively, H; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively benzyl; alternatively, an alkoxy; alternatively, an aryloxy; alternatively, acetylacetonate; alternatively, an alkylaminyl; alternatively, a dialkylamino; alternatively, a trihydrocarbylsilyl; or alternatively, a hydrocarbylaminylsilyl. In these and other aspects, alkoxy, aryloxy, alkylaminyl, dialkylamino, trihydrocarbylsilyl and hydrocarbonylanylsilyl can be alkoxy, aryloxy, alkylamino, dialkylamino, trihydrocarbylsilyl and hydrocarbylamino-silyl C1 to C36, C1 to C18, C1 to C12 or C1 to C ⁸ .

In addition, each X may independently be, in certain aspects, a halide or a C1 to C18 hydrocarbyl group; alternatively, a halide or a C1 to C ⁸ hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl or phenyl; alternatively, Cl, methyl, benzyl or phenyl; alternatively, an alkoxy, aryloxy, alkylaminyl, dialkylamino, trihydrocarbylsilyl or C 1 to C 18 hydrocarbonylamino group; alternatively, an alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl or C1 to C ⁸ hydrocarbonylamino group; or alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl , triisopropylsilyl, triphenylsilyl or allyldimethylsilyl.

In formula ( A ), CpA and CpB can independently be a substituted or unsubstituted indenyl or cyclopentadienyl group. In one aspect, CpA and CpB can independently be a non-indenyl or cyclopentadienyl group. replaced. Alternatively, CpA and CpB can independently be a substituted cyclopentadienyl or indenyl group, for example, with up to 5 substituents.

If each substituent CpA and CpB can be independently H, a halide, a hydrocarbyl group Ci to C ^36, hydrocarbyl group halogenated C ¹ to C ^36, a group hydrocarboxy C ¹ to C ^36, or hydrocarbylsilyl group C ¹ to C ³⁶ . It should be noted that each substituent in CpA and / or CpB may be the same or a different substituent group. In addition, each substituent can be found at any position in the respective cyclopentadienyl or indenyl ring structure according to the chemical valence rules. In one aspect, the number of substituents in CpA and / or in CpB and / or the positions of each substituent in CpA and / or CpB do not depend on each other. For example, two substituents or more in

CpA may be different or, alternatively, each substituent in CpA may be the same. Additionally or alternatively, two or more substituents in CpB may be different or, alternatively, all substituents in CpB may be the same. In another aspect, one or more of the substituents in CpA may be different than one or more substituents in CpB or, alternatively, all substituents in both CpA and CpB may be the same. In these and other aspects, each substituent can be found in any position in the respective indenyl or cyclopentadienyl ring structure. If substituted, CpA and / or CpB could independently have one substituent, two substituents, three substituents, four substituents, etc.

In formula (A), each substituent on CpA and / or CpB can be independently H, a halide, a hydrocarbyl group C ¹ to C ^36, hydrocarbyl group halogenated C ¹ to C ^36, a group hydrocarboxy C ¹ to C ³⁶ , or a C ¹ to C ³⁶ hydrocarbylsilyl group. In some aspects, each substituent can independently be H; alternatively, a halide; alternatively, a C ¹ to C ¹⁸ hydrocarbyl group; alternatively, a halogenated C ¹ hydrocarbyl group at

C ¹⁸ ; alternatively, a C ¹ to C ¹⁸ hydrocarboxy group; alternatively, a C ¹ to C ¹⁸ hydrocarbylsilyl group; alternatively, a C ¹ to C ¹² hydrocarbyl group or a C ¹ to C ¹² hydrocarbylsilyl group; or alternatively, a C ¹ to C ⁸ alkyl group or a C ³ to C ⁸ alkenyl group. The halide, the C ¹ to C ³⁶ hydrocarbyl group, the gr and the C ¹ to C ³⁶ hydrocarbylsilyl group, which can be a substituent in CpA and / or in CpB in the formula ( A ) can be any halide, C hydrocarbyl group ¹ to C ³⁶ hydrocarboxy group C ¹ to C ³⁶ and hydrocarbylsilyl group C ¹ to C ^36, described herein (for example, belonging to X in formula (a)). A substituent in CpA and / or CpB in the formula ( A ) may be, in certain aspects, a halogenated hydrocarbyl group C1 to C36, where the halogenated hydrocarbyl group indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbyl group. The halogenated hydrocarbyl group can often be a halogenated alkyl group, a halogenated alkenyl group, a halogenated cycloalkyl group, a halogenated aryl group or a halogenated aralkyl group. Representative and non-limiting halogenated hydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF3) and the like.

As a non-limiting example, if any, each substituent in CpA and / or CpB can independently be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg, t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group , a nonenyl group, a decenyl group, a phenyl group, a tolyl group (or other substituted aryl group), a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group; alternatively, H; alternatively, Cl; alternatively, CF3; alternatively, a methyl group; alternatively, an ethyl group; alternatively, a propyl group; alternatively, a butyl group; alternatively, a pentyl group; alternatively, a hexyl group; alternatively, a heptyl group; alternatively, an octyl group; alternatively, a nonyl group; alternatively, a decyl group; alternatively, an ethenyl group; alternatively, a propenyl group; alternatively, a butenyl group; alternatively, a pentenyl group; alternatively, a hexenyl group; alternatively, a heptenyl group; alternatively, an octenyl group; alternatively, a nonenyl group; alternatively, a decenyl group; alternatively, a phenyl group; alternatively, a tolyl group; alternatively, a benzyl group; alternatively, a naphthyl group; alternatively, a trimethylsilyl group; alternatively, a triisopropylsilyl group; alternatively, a triphenylsilyl group; or alternatively, an allyldimethylsilyl group.

Illustrative non-limiting examples of metallocene compounds without bridges with formula ( A ) and / or suitable for use as catalyst component I may include the following compounds:

and the like, as well as combinations of these.

Additional examples of metallocene compounds without bridges with formula (A) and / or suitable for use as catalyst component I may include the following compounds, but not limited to these:

and the like, as well as combinations of these.

Additional non-limiting examples of metallocene compounds without bridges with formula (A) and / or suitable for use as catalyst component I may include the following compounds:

and the like, as well as combinations of these.

The catalytic component I is not limited only to metallocene compounds without bridges such as those described above. For example, the catalytic component I may comprise a dinuclear metallocene compound based on hafnium and / or zirconium without bridges. In one aspect, the catalytic component I may comprise a zirconium-based homodinuclear metallocene compound without bridges. In another aspect, the catalytic component I may comprise a homodinuclear metallocene compound based on hafnium without bridges. In even another aspect, the catalytic component I may comprise a heterodinuclear metallocene compound based on hafnium and / or zirconium without bridges (i.e., a dinuclear compound with two hafnia or two zirconia, or a zirconium and a hafnium). The catalytic component I may comprise non-bridged dinuclear metallocenes such as those described in US Pat. Nos. 7,919,639 and 8,080,681. Non-limiting illustrative examples of dinuclear metallocene compounds suitable for use as catalyst component I may include the following compounds:

and the like, as well as combinations of these.

Catalytic Component II

The catalytic component II may comprise a zirconium-based metallocene compound with bridges with a fluorenyl group and without any aryl group in the bridge group. In one aspect, for example, the catalytic component II may comprise a zirconium-based metallocene compound with bridges with a cyclopentadienyl group and a fluorenyl group and without any aryl group in the bridge group. In another aspect, the catalytic component II may comprise a metallocene compound with bridges with the formula ( B ):

In formula ( B ), CpC, each X, E ² , RX and RY are independent elements of the metallocene compound with bridges. Accordingly, the metallocene compound with bridges of formula ( B ) can be described using any combination of CpC, X, E ² , RX and RY described herein.

The selections for each X in the formula ( B ) are the same as those described hereinbefore for the formula ( A ). In formula ( B ), CpC can be a substituted cyclopentadienyl, indenyl or fluorenyl group. In one aspect, CpC can be a substituted cyclopentadienyl group, while, in another aspect, CpC can be a substituted indenyl group.

In some aspects, CpC may not contain additional substituents, for example, other than the E ² group that forms bridges, discussed further hereinafter. In other aspects, CpC can be further substituted with a substituent, two substituents, three substituents, four substituents, etc. If each substituent ToT can be independently H, a halide, a hydrocarbyl group Ci to C ^36, hydrocarbyl group halogenated C ¹ to C ^36, a group hydrocarboxy C ¹ to C ^36, or hydrocarbylsilyl group C ¹ to C ³⁶ . It should be noted that each substituent in CpC can be the same or a different substituent group. In addition, each substituent can be found at any position in the respective cyclopentadienyl, indenyl or fluorenyl ring structure according to the chemical valence rules. In general, any substituent on ToT independently can be H or any halide, the hydrocarbyl group C ¹ to C ^36, hydrocarbyl group halogenated C ¹ to C ^36, the hydrocarboxy C ¹ group to C ^36, or hydrocarbylsilyl group C ¹ to C ³⁶ , described herein (for example, belonging to the substituents in CpA and CpB in the formula ( A )).

In one aspect, for example, each CpC substituent can independently be a C ¹ to C ¹² hydrocarbyl group or a C ¹ to C ¹² hydrocarbylsilyl group. In another aspect, each CpC substituent can independently be a C ¹ to C ⁸ alkyl group or a C ³ to C ⁸ alkenyl group. In even another aspect, each CpC substituent can independently be H, Cl, CF ³ , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group , a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group.

Similarly, Rxy RYEN formula (B) may be independently H or any halide, the hydrocarbyl group C ¹ to C ^36, hydrocarbyl group halogenated C ¹ to C ^36, the hydrocarboxy C ¹ group to C ³⁶ or hydrocarbylsilyl group C ¹ to C ³⁶ , described herein (for example, belonging to the substituents in CpA and CpB in the formula ( A )). In one aspect, for example, RX and RY can independently be H or a C1 to C12 hydrocarbyl group. In another aspect, RX and RY can independently be a C1 to C10 hydrocarbyl group. In even another aspect, RX and RY can independently be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg, t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group , a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group, and the like. In yet another aspect, RX and RY can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group , an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group or a benzyl group.

The bridge group E ² in formula ( B ) can be (i) a bridge group with the formula> EARARB, where EA can be C, Si or Ge, and RA and RB can independently be H or a C1 hydrocarbyl group to C18, (ii) a bridge group with the formula -CRCRD-CRERF-, where RC, RD, RE and RF can independently be H or a hydrocarbyl group C1 to C18 or (iii) a bridge group of formula - SiRGRH-E ⁵ RRJ-, where E ⁵ can be C or Si, and RG, RH, RI and RJ independently can be H or a C1 to C18 hydrocarbyl group. In these formulas, RA, RB, RC, RD, RE, RF, RG, RH, RI and RJ are not aryl groups.

In the first option, the bridge group E2 can have the formula> EARARB, where EA can be C, Si or Ge, and RA and RB can independently be H or any hydrocarbyl group Ci to C i8 described herein ( that is, different from an aryl group). In some aspects of this invention, RA and RB can independently be a C1 to C12 hydrocarbyl group; alternatively, RA and RB can independently be a C1 to C8 hydrocarbyl group; alternatively, RA and RB can independently be a C1 to C8 alkyl group or a C3 to C8 alkenyl group; alternatively, RA and RB can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a group ethenyl, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, or a decenyl group; or alternatively, RA and RB can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group or a hexenyl group. In these and other aspects, RA and RB may be the same or different. In the second option, the bridge group E2 can have the formula -CRCRD-CRERF-, where RC, RD, RE and RF can independently be H or any C1 to C18 hydrocarbyl group described herein (ie, different of an aryl group). For example, RC, RD, RE and RF can independently be H or a methyl group.

In the third option, the bridge group E2 can have the formula -SiRGRH-E5RRJ-, where E5 can be C or Si, and RG, RH, R1 and RJ can independently be H or any C1 to C18 hydrocarbyl group described in the present memory (ie, different from an aryl group). For example, E5 can be Si, and RG, RH, R1 and RJ can independently be H or a methyl group.

Non-limiting illustrative examples of metallocene compounds with bridges with formula ( B ) and / or suitable for use as catalyst component II may include the following compounds (Me = methyl, t-Bu = tert-butyl):

and the like, as well as combinations of these.

Additional examples of metallocene compounds with bridges with formula (B) and / or suitable for use as catalyst component II may include the following compounds, but not limited to these:

and the like, as well as combinations of these.

Catalytic Component III

The catalytic component III may comprise a zirconium or hafnium-based metallocene compound with bridges with a fluorenyl group and an aryl group in the bridge group. In one aspect, for example, the catalytic component III may comprise a zirconium or hafnium-based metallocene compound with bridges with a cyclopentadienyl group and a fluorenyl group and an aryl group in the bridge group. In another aspect, the catalytic component III may comprise a zirconium-based metallocene compound with bridges with a fluorenyl group and an aryl group in the bridge group, while in yet another aspect, the catalytic component III may comprise a metallocene compound based on hafnium with bridges with a fluorenyl group and an aryl group in the bridge group. In these and other aspects, the aryl group in the bridge group may be a phenyl group.

The catalytic component III may comprise a bridged metallocene compound with the formula ( C ) in certain aspects of this invention:

In formula ( C ), M ³ , CpC, RX, RY, E ³ , each R ³ , and each X are independent elements of the bridged metallocene compound. Accordingly, the metallocene compound with bridges of formula ( C ) can be described using any combination of M ³ , CpC, RX, RY, E ³ , R ³ and X described herein.

As noted above and unless otherwise specified, formula ( C ) above, any other structural formulas described herein and any complex, compound or species of metallocene (or dinuclear metallocene) described herein are not designed to show the stereochemistry or the isomeric position of the different moieties (for example, it is not intended that these formulas present the cis or trans isomers, or the R or S diastereomers), although said formulas and / or structures contemplate and encompass said compounds.

The selections for CpC, RX, RY and each X in the formula ( C ) are the same as those described hereinbefore for the formula ( B ). Therefore, in formula ( C ), CpC can be a substituted cyclopentadienyl, indenyl or fluorenyl group. In some aspects, CpC may be a substituted cyclopentadienyl group, while, in other aspects, CpC may be a substituted indenyl group. CpC may not contain additional substituents, for example, other than the bridge group E ³ , discussed further hereinafter. Alternatively, CpC can be further substituted with a substituent, two substituents, three substituents, four substituents, etc. If there is, each substituent in CpC can independently be H, a halide, a Ci to C ³⁶ hydrocarbyl group, a C ¹ to C ³⁶ halogenated hydrocarbyl group, a C ¹ to C ³⁶ hydrocarboxy group or a C ¹ to C ³⁶ hydrocarbylsilyl group . It should be noted that each substituent in CpC can be the same or a different substituent group. In addition, each substituent can be found at any position in the respective cyclopentadienyl, indenyl or fluorenyl ring structure according to the chemical valence rules. In general, any CpC substituent, independently, can be H or any halide, C ia C36 hydrocarbyl group, Ci to C36 halogenated hydrocarbyl group, C ¹ to C ³⁶ hydrocarboxy group or C ¹ to C ³⁶ hydrocarbylsilyl group, described herein. memory (for example, belonging to the substituents in CpA and CpB in the formula ( A )).

In one aspect, for example, each CpC substituent can independently be a C ¹ to C ¹² hydrocarbyl group or a C ¹ to C ¹² hydrocarbylsilyl group. In another aspect, each substituent may be independently a CpC alkyl C1 to Cs alkenyl group or C3 to ^C8. In even another aspect, each CpC substituent can independently be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a group tolyl, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group.

As in the formula ( B ), RX and RY in the formula ( C ) can independently be H or any halide, hydrocarbyl group C1 to C36, halogenated hydrocarbyl group C1 to C36, hydrocarboxy group C1 to C36 or hydrocarbylsilyl group C1 to C ³⁶ , described herein (for example, belonging to the substituents in CpA and CpB in the formula ( A )). In one aspect, for example, RX and RY can independently be H or a C ¹ to C ¹² hydrocarbyl group. In another aspect, RX and RY can independently be a C ¹ to C ¹⁰ hydrocarbyl group. In even another aspect, RX and RY can independently be H, Cl, CF ³ , a methyl group, an ethyl group, a propyl group, a butyl group (eg, t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a group Decenyl, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group, and the like. In yet another aspect, RX and RY can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a group ethenyl, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group or a benzyl group.

As in the formula (A), each X in the formula (C) can independently be H, BH ⁴ or any halide, hydrocarbyl group Ci to C ³⁶ , hydrocarboxy group Ci to C ³⁶ , hydrocarbylaminyl group Ci to C ³⁶ , hydrocarbylsilyl group Ci to C36, or Ci to C36 hydrocarbylaminylsilyl group, described herein, or -OBR12 or -OSO2R1, wherein R ¹ is any Ci to C36 hydrocarbyl group described herein. For example, each X can independently be a halide or a hydrocarbyl group Ci to C ^{i 8} . In a particular aspect, each X can be Cl.

According to aspects of this invention, the metal in the formula (C), M ³ , can be Zr or Hf. In one aspect, for example, M ³ can be Zr, while in another aspect, M ³ can be Hf. The bridge atom E ³ can be C, Si or Ge, and each R ³ independently can be H or any hydrocarbyl group Ci to C ⁱ⁸ described herein, however, at least one R ³ is an aryl group having up to i8 carbon atoms. In some aspects, the bridge atom E ³ may be C and, additionally or alternatively, one R ³ may be a phenyl group and the other R ³ may be a Ci to C ⁸ alkyl group or a C ³ to C ⁸ alkenyl group . For example, each R ³ can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a cyclohexylphenyl group, a naphthyl group, a tolyl group or a benzyl group, wherein at least one R ³ is an aryl group (for example, a phenyl group). In some aspects, each R ³ can be a phenyl group.

Illustrative non-limiting examples of metallocene compounds with bridges with formula (C) and / or suitable for use as catalyst component III may include the following compounds (Ph = phenyl):

2i

and the like, as well as combinations of these.

Activating brackets

The present description encompasses several catalyst compositions containing an activator, such as an activating support. In one aspect, the activating support may comprise a chemically treated solid oxide. Alternatively, in another aspect, the activating support may comprise a clay mineral, a pillarized clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a stratified silicate mineral, a non-stratified silicate mineral, a mineral of stratified aluminosilicate, a non-stratified aluminosilicate mineral or combinations thereof.

Generally, chemically treated solid oxides have increased acidity compared to the corresponding untreated solid oxide compound. The chemically treated solid oxide can also function as a catalyst activator compared to the corresponding untreated solid oxide. Although chemically treated solid oxide can activate a metallocene complex in the absence of cocatalysts, it is not necessary to remove cocatalysts from the catalytic composition. The activation function of the activating support can increase the activity of the catalytic composition as a whole, compared to a catalytic composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator, even in the absence of an organoaluminum compound, aluminoxanes, organoboro or organoborate compounds, ionizing ionic compounds and the like.

The chemically treated solid oxide may comprise a solid oxide treated with an electron acceptor anion. Although the link to the following statement is not intended, it is believed that the treatment of the solid oxide with an electron acceptor component increases or increases the acidity of the oxide. Thus, either the activating support has Lewis or Bransted acidity that is typically greater than the Lewis or Bronsted acid strength of the untreated solid oxide or the activating support has a greater number of acid sites than the untreated solid oxide, or both of them. One method to quantify the acidity of chemically treated and untreated solid oxides materials may be to compare the polymerization activities of the treated and untreated oxides in acid catalyzed reactions.

Chemically treated solid oxides can generally be formed from an inorganic solid oxide that exhibits Lewis acid or Bransted acid behavior and has a relatively high porosity. The solid oxide can be chemically treated with an electron acceptor component, typically an electron acceptor anion, to form an activating support.

According to one aspect, the solid oxide used to prepare the chemically treated solid oxide may have a pore volume greater than about 0.1 cm ³ / g. According to another aspect, the solid oxide may have a pore volume greater than about 0.5 cm ³ / g. According to another aspect, the solid oxide can have a pore volume greater than about 1.0 cm ³ / g.

In another aspect, the solid oxide may have a specific surface area of about 100 m ² / g or about 1000 m ² / g. In yet another aspect, the solid oxide may have a specific surface area of about 200 m ² / g or about 800 m ² / g. In yet another aspect of the present invention, the solid oxide may have a specific surface area of about 250 m ² / g to about 600 m ² / g.

The chemically treated solid oxide may comprise an inorganic solid oxide comprising oxygen and one or more elements selected from group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table or comprising oxygen and one or more elements selected from the lanthanide or actinide elements (see: Condensed Chemical Dictionary of Hawley, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide may comprise oxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.

Suitable examples of solid oxides materials or compounds that can be used to form the chemically treated solid oxide may include: A ^ O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2Os, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2 and the like, but not limited to these, including mixed oxides of these and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolitungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides of these or any combination of these .

The solid oxide encompasses oxidic materials such as alumina, "mixed oxides" thereof such as silica-alumina, materials in which one oxide is coated with another, as well as any combination and mixture thereof. The mixed oxide compounds such as silica-alumina can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activating support, alone or in combination, may include silica-alumina, silica-titania, silica-zirconia, zeolites, various clay minerals, alumina-titania, alumina-zirconia, zinc aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia and the like, but not limited to these. The solid oxide of this invention also encompasses oxidic materials such as silica coated alumina, as described in US Patent No. 7,884,163.

The electron acceptor component used to treat the solid oxide can be any component that increases the Lewis or Bransted acidity of the solid oxide after treatment (compared to the solid oxide that is not treated with at least one electron acceptor anion). In accordance with one aspect of the present invention, the electron acceptor component may be an electron acceptor anion derived from a salt, an acid or other compound, such as a volatile organic compound, which serves as a source or precursor of that anion. Examples of electron acceptor anions may include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorocirconate, fluorotitanate, phosphotungstate, but not limited to these, and the like, including mixtures and combinations of these. In addition, other ionic or non-ionic compounds that serve as sources for these acceptor anions can also be employed in the present invention. of electrons It is contemplated that the electron acceptor anion may be, or may comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate or sulfate and the like, or any combination thereof, in some aspects of this invention. In other aspects, the electron acceptor anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorocirconate, fluorotitanate, and the like, or combinations thereof.

Thus, for example, the activating support (eg, chemically treated solid oxide) used in the catalyst compositions of the present invention may be, or may comprise, fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, silica-alumina fluorinated, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphated silica, and the like, or combinations thereof. In one aspect, the activating support may be, or may comprise, fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica coated alumina, sulfated silica coated alumina, phosphate silica coated alumina, and the like , or any combination of these. In another aspect, the activating support may comprise fluorinated alumina; alternatively, chlorinated alumina; alternatively, sulfated alumina; alternatively, fluorinated silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia; or alternatively, alumina coated with fluorinated silica.

When the electron acceptor component comprises a salt of an electron acceptor anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert to the acid, or decompose in the acid, during calcination. Factors that dictate the suitability of the particular salt to serve as a source for the electron acceptor anion may include the solubility of the salt in the desired solvent, the absence of adverse reactivity of the cation, the effects of ion matching between the cation and the anion, the hygroscopic properties conferred on the salt by the cation, but not limited to these, and the like, and the thermal stability of the anion. Examples of suitable cations in the electron acceptor anion salt may include ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H +, [H (OEt2) 2] +, but not limited to these, and the like.

In addition, combinations of one or more different electron acceptor anions may be used, in varying proportions, to adjust the specific acidity of the activating support to the desired level. The combinations of electron acceptor components can be contacted with the oxide material simultaneously or individually, and in any order, which gives the desired acidity of the chemically treated solid oxide. For example, in one aspect of this invention two or more electron-accepting anion source compounds may be employed in two or more separate contact steps.

Thus, a process by which a chemically treated solid oxide can be prepared is as follows: a selected solid oxide, or a combination of solid oxides, is contacted with a first electron acceptor anion source compound to form a first mixture ; this first mixture can be calcined and then contacted with a second electron acceptor anion source compound to form a second mixture; The second mixture can then be calcined to form a treated solid oxide. In said process, the first and second electron source acceptor anion compounds are either the same compound or different compounds.

According to another aspect, the chemically treated solid oxide may comprise a solid inorganic oxide material, a mixed oxide material or a combination of inorganic oxide materials, which is chemically treated with an electron acceptor component and optionally treated with a source of metal, including metal salts, metal ions or other compounds containing metal. Non-limiting examples of the metal or metal ion may include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium and the like or combinations thereof. Examples of chemically treated solid oxides containing a metal or metal ion may include chlorinated alumina impregnated with zinc, fluorinated alumina impregnated with titanium, fluorinated alumina impregnated with zinc, chlorinated silica-alumina impregnated with zinc, silica-fluorinated alumina impregnated with zinc, zinc impregnated sulfate alumina, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, silica coated alumina treated with hexafluorotitannic acid, alumina coated with zinc treated silica and then fluorinated, but not limited to these, and the like, or any combination of these.

Any method can be used to impregnate the solid oxide material with a metal. The method by which the oxide is contacted with a metal source, typically a metal-containing salt or compound, may include gelation, cogelification, impregnation of one compound into another, but not limited to these, and the like. If desired, the metal-containing compound may be added to the solid oxide, or it may be impregnated in the solid oxide, in the form of a solution and subsequently converted into a support metal with calcination. Accordingly, the inorganic solid oxide may further comprise a metal selected from: zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum and the like or combinations of these metals. For example, zinc can often be used to impregnate the solid oxide because it can provide improved catalytic activity at a low cost.

The solid oxide can be treated with metal salts or compounds containing metal before it is treated, after it is treated, or at the same time it is treated, the solid oxide with the electron acceptor anion. After any contact method, the contact mixture of solid compound, anion acceptor anion can be calcined electrons and the metal ion. Alternatively, a solid oxide material, an electron acceptor anion source and the metal salt or the metal-containing compound can be contacted and calcined simultaneously.

Various methods can be used to form the chemically treated solid oxide useful in the present invention. The chemically treated solid oxide may comprise the contact product of one or more solid oxides with one or more sources of electron acceptor anion. The solid oxide is not required to calcine before contacting the electron acceptor anion source. Typically, the contact product can be calcined either during the contacting, or after contacting, of the solid oxide with the electron acceptor anion source. The solid oxide can be calcined or not. Several methods for preparing solid oxide activating supports that can be used in this invention have been indicated. For example, such methods are described in US Patents Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,676,5,6,6,774, 6,676,567, 6,676,567, 6,676,567

According to one aspect, the solid oxide material can be chemically treated by contacting it with an electron acceptor component, typically a source of electron acceptor anion. In addition, the solid oxide material can optionally be chemically treated with a metal ion and then calcined to form a solid oxide that contains metal or is impregnated with chemically treated metal. According to another aspect of the present invention, the solid oxide material and the electron acceptor anion source can be contacted and calcined simultaneously.

The method by which the oxide is contacted with the electron acceptor component, typically a salt or an acid of an electron acceptor anion, may include gelation, cogelification, impregnation of one compound into another, but not limited to these, and Similar. Thus, after any contact method, the contact mixture of the solid oxide, the electron acceptor anion and the optional metal ion can be calcined.

The solid oxide activating support (i.e. chemically treated solid oxide) can thus be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with an electron acceptor anion source compound (or compounds) to form a first mixture and

2) calcine the first mixture to form the solid oxide activating support.

According to another aspect of the present invention, the solid oxide activating support (chemically treated solid oxide) can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with a first electron acceptor anion source compound to form a first mixture;

2) calcine the first mixture to produce a first calcined mixture;

3) contacting the first calcined mixture with a second electron acceptor anion source compound to form a second mixture and

4) calcine the second mixture to form the solid oxide activating support.

According to yet another aspect, the chemically treated solid oxide can be produced or formed by contacting the solid oxide with the electron acceptor anion source compound, where the solid oxide compound is calcined before contacting, during contacting, or after contacting, with the source of electron acceptor anion and where there is a substantial absence of aluminoxanes, organoboro or organoborate compounds and ionizing ionic compounds.

The calcination of the treated solid oxide is generally carried out in an ambient atmosphere, typically in a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C and for a time of about 1 minute to about 100 hours. The calcination can be carried out at a temperature in the range of about 300 ° C to about 800 ° C, or alternatively, at a temperature in the range of about 400 ° C to about 700 ° C. The calcination can be carried out during a time interval between approximately 30 minutes and approximately 50 hours or during a time interval between approximately 1 hour and approximately 15 hours. Thus, for example, calcination can be carried out for a period of time from about 1 hour to about 10 hours at a temperature in the range of about 350 ° C to about 550 ° C. Any suitable ambient atmosphere can be used during calcination. Generally, calcination can be carried out in an oxidizing atmosphere, such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.

According to one aspect, the solid oxide material can be treated with a source of halide ion, sulfate ion or a combination of anions, optionally treated with a metal ion, and then calcined to provide the oxide chemically treated solid in the form of a particulate solid. For example, the solid oxide material can be treated with a sulfate source (called a "sulphating agent"), a source of bromide ion (called a "brominating agent"), a source of chloride ion (called a "chlorinating agent" ), a source of fluoride ion (called a "fluorinating agent") or a combination thereof, and calcined to provide the solid oxide activator. Useful acidic activating supports may include brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, silica-fluorinated alumina, silica-sulfated alumina, silica-brominated zirconia, silica-chlorinated zirconia, silica - fluorinated zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina treated with hexafluorotitannic acid, alumina coated with silica treated with hexafluorotitanic acid, silica alumina treated with hexafluorocirconic acid, silica-alumina treated with trifluoroacetic silica, trifluoroacetic acid silica, trifluoroacetic silica treated, trifluoroacetic silica with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillarized clay, such as pillarized montmorillonite, optionally treated with fluoride, chloride or sulfate; phosphate alumina or other aluminophosphates optionally treated with sulfate, fluoride or chloride, but not limited to these; or any combination of the above. In addition, any of these activator supports can be optionally treated or impregnated with a metal ion.

In one aspect, the chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. The fluorinated solid oxide can be formed by contacting a solid oxide with a fluorinating agent. The fluoride ion can be added to the oxide by forming a suspension of the oxide in a suitable solvent such as alcohol or water including alcohols of one to three carbons, but not limited to these, due to its volatility and low surface tension. Examples of suitable fluoridating agents may include hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4) 2SiFaor), hexaphosphate of ammonium (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4) 2TiFa), hexafluorocirconic acid (H2ZrFa), AF 3, NH4A F 4, but not limited to these, analogues thereof, and combinations thereof. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluoridating agent, due to its ease of use and availability.

If desired, the solid oxide can be treated with a fluorinating agent during the calcination step. Any fluorinating agent capable of completely contacting the solid oxide can be used during the calcination step. For example, in addition to the previously described fluoridating agents, volatile organic fluoridating agents can be used. Examples of volatile organic fluoridating agents useful in this regard may include freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, but not limited to these, and the like, and combinations thereof. Calcination temperatures should, in general, be high enough to decompose the compound and release fluoride. Gaseous hydrogen fluoride (HF) or fluorine (F2) itself can also be used with the solid oxide if it is fluoridated while calcining. Silicon tetrafluoride (SF 4) and compounds containing tetrafluoroborate (BF4 ') can also be used. A convenient method of contacting the solid oxide with the fluorinating agent may be to vaporize a fluorinating agent in a gas stream used to fluidize the solid oxide during calcination.

Similarly, in another aspect, the chemically treated solid oxide may comprise a chlorinated solid oxide in the form of a particulate solid. The chlorinated solid oxide can be formed by contacting a solid oxide with a chlorinating agent. The chloride ion can be added to the oxide by forming a suspension of the oxide in a suitable solvent. The solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a source of chloride and being completely in contact with the oxide can be used during the calcination step, such as SiCU, SiMe2Cl2, TiCU, BCl3, and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents include certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, but not limited to these, and the like, or any combination thereof. Gaseous hydrogen chloride or chlorine itself can also be used with the solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent may be to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.

The amount of fluoride or chloride ion present before the calcination of the solid oxide can generally be between about 1% and about 50%, by weight, where the weight percentage is based on the weight of the solid oxide, for example, silica-alumina, before calcination. According to another aspect, the amount of fluoride or chloride ion present before the calcination of the solid oxide can be between about 1% and about 25%, by weight, and according to another aspect of this invention, between about 2% and about 20 %, in weigh. According to another aspect, the amount of fluoride or chloride ion present before the calcination of the solid oxide can be between about 4% and about 10%, by weight. Once impregnated with the halide, the halogenated oxide can be dried by any suitable method including suction filtration followed by evaporation, vacuum drying, spray drying, but not limited to these, and the like, although it is also possible to start the calcination step. immediately without drying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina can typically have a pore volume greater than about 0.5 cm ³ / g. According to one aspect, the pore volume may be greater than about 0.8 cm ³ / g and according to another aspect, greater than about 1.0 cm ³ / g. In addition, silica-alumina can generally have a specific surface area greater than about 100 m ² / g. According to another aspect, the surface Specific may be greater than about 250 m2 / g. According to another aspect, the specific surface area may be greater than approximately 350 m2 / g.

The silica-alumina used in the present invention can typically have an alumina content between about 5% and about 95%, by weight. According to one aspect, the alumina content of the silica alumina can be between about 5% and about 50%, by weight, or between about 8% and about 30%, of alumina, by weight. According to another aspect, silica alumina compounds with a high alumina content can be employed, in which the alumina content of these silica alumina compounds typically ranges from about 60% to about 90% or from about 65% to about 80% , alumina, by weight. According to another aspect of this invention, the solid oxide component may comprise alumina without silica, and according to another aspect of this invention, the solid oxide component may comprise silica without alumina.

The sulfated solid oxide may comprise sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide can also be treated with a metal ion so that the calcined sulfated oxide comprises a metal. According to one aspect, the sulfated solid oxide may comprise sulfate and alumina. In some cases, sulfated alumina can be formed by a process in which alumina is treated with a sulfate source, for example, sulfuric acid or a sulfate salt such as ammonium sulfate. This process can generally be carried out by forming a suspension of the alumina in a suitable solvent, such as alcohol or water, in which the desired concentration of the sulphating agent has been added. Suitable organic solvents may include alcohols of one to three carbons, but not limited to these, due to their volatility and low surface tension.

According to one aspect, the amount of sulfate ion present before calcination can be from about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. According to another aspect of this invention, the amount of sulfate ion present before calcination can be from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide and according to another aspect of this invention, of about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of the solid oxide before calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method including suction filtration followed by evaporation, vacuum drying, spray drying, but not limited to these, and the like, although it is also possible to start the calcination step immediately. .

According to another aspect, the activating support used to prepare the catalytic compositions of this invention may comprise an ion exchange activating support, including silicate and aluminosilicate compounds or minerals, but not limited to these, either with stratified structures or not, and combinations of these. In another aspect, stratified aluminosilicates with ion exchange, such as pillarized clays, can be used as activating supports. When the acid activating support comprises an ion exchange activating support, it may optionally be treated with at least one electron acceptor anion such as those described herein, although typically the ion exchange activating support is not treated with an acceptor anion. of electrons

According to another aspect, the activating support of this invention may comprise clay minerals that have interchangeable cations and layers capable of expanding. Typical clay ore activating supports may include stratified aluminosilicates with ion exchange such as pillarized clays, but not limited to these. Although the term "support" is used, it is not intended to be considered as an inert component of the catalytic composition, but can be considered an active part of the catalytic composition, due to its intimate association with the metallocene component.

According to another aspect, the clay materials of this invention may encompass materials either in their natural state or that have been treated with various ions by wetting, ion exchange or pillarization. Typically, the clay material activating support of this invention may comprise clays that have undergone ion exchange with large cations, including highly charged polynuclear metal complex cations. However, the clay material activating supports of this invention may also encompass clays that have undergone ion exchange with simple salts, including salts of Al (III), Fe (II), Fe (III) and Zn (II ) with ligands such as halide, acetate, sulfate, nitrate or nitrite, but not limited to these.

According to another aspect, the activating support can comprise a pillarized clay. The term "pillarized clay" is used to refer to clay materials that have undergone ion exchange with typically highly polynuclear, highly charged, highly complex metal cations. Examples of such ions may include Keggin ions that may have charges such as 7+, various polyoxomethalates and other large ions, but not limited to these. Thus, the term "pillarization" may refer to a simple exchange reaction in which the exchangeable cations of a clay material are replaced with large highly charged ions, such as Keggin ions. These polymeric cations can then be immobilized in the clay interlayers and when calcined they become "pillars" of metal oxide, which effectively support the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between the layers of clay, the expanded framework structure can be maintained and the porosity can be increased. The resulting pores may vary in shape and size as a function of the pillar material and the precursor clay material used. Examples of pillarization and pillarized clays are found in: TJ Pinnavaia, Science 220 (4595), 365-371 (1983); JM Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Chap. 3, pp.

55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No.

5,376,611 and U.S. Patent No. 4,060,480.

The pillarization process can use clay minerals that have interchangeable cations and layers capable of expanding. Any pillarized clay that can increase the polymerization of olefins in the catalytic composition can be used. Therefore, clay minerals suitable for pillarization may include allophanes; smectites, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof such as montmorillonites (bentonites), nontronites, hectorites or laponites; haloisites; vermiculites; micas; fluoromics; chlorites; mixed layer clays; fibrous clays including sepiolites, attapulgites and paligorskites, but not limited to these; a serpentine clay; ilita; laponite; saponite; but not limited to these, and any combination of these. In one aspect, the pillarized clay activating support may comprise bentonite or montmorillonite. The main component of bentonite is montmorillonite.

Pilarized clay can be pretreated if desired. For example, a pillarized bentonite can be pretreated by drying at about 300 ° C in an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although exemplary pretreatment is described herein, it should be understood that preheating can be performed at many other temperatures and times, including any combination of temperature and time stages, all of which are encompassed by this invention.

The activating support used to prepare the catalyst compositions may be combined with other inorganic support materials, including zeolites, inorganic oxides, phosphate inorganic oxides, but not limited to these, and the like. In one aspect, typical support materials that can be used include silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, toria, aluminophosphate, aluminum phosphate, silica-titania, co-precipitated silica / titania, but not limited to to these, mixtures of these, or any combination of these.

According to another aspect, one or more of the metallocene compounds can be previously contacted with an olefinic monomer and an organoaluminum compound for a first period of time before contacting this mixture with the activating support. Once the previously contacted mixture of the complex or complexes of metallocene, olefinic monomer and organoaluminum compound is contacted with the activating support, the composition further comprising the activating support may be referred to as the "post-contacted" mixture. . The subsequently contacted mixture may be allowed to remain in additional contact for a second period of time before loading it into the reactor in which the polymerization process will be carried out.

According to another aspect, one or more of the metallocene compounds can be previously contacted with an olefinic monomer and an activating support for a first period of time before contacting this mixture with the organoaluminum compound. Once the previously contacted mixture of the metallocene complex or complexes, olefinic monomer and activating support is contacted with the organoaluminum compound, the composition further comprising the organoaluminum may be referred to as the "subsequent contacting" mixture. The subsequently contacted mixture may be allowed to remain in additional contact for a second period of time before being introduced into the polymerization reactor.

Cocatalysts

In certain aspects directed to catalytic compositions containing a cocatalyst, the cocatalyst may comprise a metal hydrocarbyl compound, examples of which include metal hydrocarbyl compounds other than halide, metal hydrocarbyl halide compounds, metal alkyl compounds other than halide, metal alkyl halide compounds, etc. The hydrocarbyl group (or alkyl group) may be any hydrocarbyl (or alkyl) group described herein. In addition, in some aspects, the metal of the metal hydrocarbyl can be a group 1, 2, 11, 12, 13 or 14 metal; alternatively, a metal of group 13 or 14; or alternatively, a group 13 metal. Therefore, in some aspects, the metal of the metal hydrocarbyl (metal hydrocarbyl other than halide or metal hydrocarbyl halide) may be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminum or tin; alternatively, lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum or tin; alternatively, lithium, sodium or potassium; alternatively, magnesium or calcium; alternatively, lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively, zinc; alternatively, boron; alternatively, aluminum or alternatively, tin. In some aspects, the hydrocarbyl metal or alkyl metal, with or without halide, may comprise an alkyl lithium hydrocarbyl, a hydrocarbyl or alkyl magnesium, a hydrocarbyl or alkyl boron, a hydrocarbyl or alkyl zinc, or an alkyl aluminum hydrocarbyl.

In particular aspects directed to catalytic compositions containing cocatalyst (for example, the activator may comprise a solid oxide treated with an electron acceptor anion), the cocatalyst may comprise an aluminoxane compound, an organoboro or organoborate compound, an ionizing ionic compound , a Organoaluminum compound, an organocinc compound, an organomagnesium compound, or an organolithium compound, and this includes any combination of these materials. In one aspect, the cocatalyst can comprise an organoaluminum compound. In another aspect, the cocatalyst can comprise an aluminoxane compound, an organoboro or organoborate compound, an ionizing ionic compound, an organocinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In yet another aspect, the cocatalyst may comprise an aluminoxane compound; alternatively, an organoboro or organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organocinc compound; alternatively, an organomagnesium compound; or alternatively, an organolithium compound.

Organoaluminum compounds

In some aspects, the catalyst compositions of the present invention may comprise one or more organoaluminum compounds. Such compounds may include compounds that have the following formula, without being limited to these,

(RZ) sAl;

where each RZ can independently be an aliphatic group that has 1 to 10 carbon atoms. For example, each RZ can independently be methyl, ethyl, propyl, butyl, hexyl or isobutyl.

Other organoaluminum compounds that can be used in the catalyst compositions described herein may include compounds having the following formula, without being limited thereto,

Al (X7) m (X8) ³ -m,

where each X7 can independently be a hydrocarbyl; each X8 can independently be an alkoxide or an aryloxide, a halide or a hydride; and m can be from 1 to 3, inclusive. Here, hydrocarbyl is used to specify a hydrocarbon radical group and includes, for example, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalcadienyl, alkynyl, aralkyl, aralkenyl and aralkynyl groups.

In one aspect, each X7 can independently be any hydrocarbyl having 1 to about 18 carbon atoms described herein. In another aspect of the present invention, each X7 can independently be any alkyl having 1 to 10 carbon atoms described herein. For example, each X7 can independently be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl or hexyl, and the like, in yet another aspect.

According to one aspect, each X8 can independently be an alkoxide or an aryloxide, any of which has 1 to 18 carbon atoms, a halide or a hydride. In another aspect of the present invention, each X8 can be independently selected from fluorine and chlorine. In yet another aspect, X8 can be chlorine.

In the formula Al (X7) m (X8) 3-m, m can be a number from 1 to 3, inclusive, and typically, m can be 3. The value of m is not limited to an integer; therefore, this formula may include sesquihalide compounds or other compounds with organoaluminic groupings.

Examples of organoaluminum compounds suitable for use in accordance with the present invention may include trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, but not limited to dialkyl aluminum hydride compounds, and combinations thereof. Specific non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-nhexylaluminum, tri- n-octylaluminum, diisobutyl aluminum hydride, diethylaluminium ethoxide, diethylaluminium chloride, and the like, or combinations thereof.

The present description contemplates a method for previously contacting a metallocene compound (or compounds) with an organoaluminum compound and an olefinic monomer to form a previously contacted mixture, before contacting this previously contacted mixture with a activating support to form a catalytic composition. When the catalyst composition is prepared in this manner, typically, although not necessarily, a portion of the organoaluminum compound may be added to the previously contacted mixture and another portion of the organoaluminum compound may be added to the subsequently brought into contact mixture when it is prepared. puts the previously contacted mixture in contact with the solid oxide activating support. However, the complete organoaluminum compound can be used to prepare the catalytic composition at the stage of either prior contact or subsequent contact. Alternatively, all catalyst components can be contacted in a single stage.

In addition, more than one organoaluminum compound may be used at the stage of either prior contact or subsequent contact. When an organoaluminum compound is added in multiple stages, the amounts of organoaluminum compound described herein include the total amount of organoaluminum compound used in the mixtures, both previously contacted and subsequently contacted, and any compound of Additional organoaluminum added to the polymerization reactor. Therefore, the quantities Total organoaluminum compounds are described regardless of whether a single organoaluminum compound or more than one is used.

Aluminoxane compounds

Certain aspects provide a catalytic composition that can comprise an aluminoxane compound. As used herein, the terms "aluminoxane" and "aluminoxane compound" refer to discrete compounds, compositions, mixtures or species of aluminoxane, regardless of how they are prepared, formed or otherwise provided. aluminoxanes. For example, a catalyst composition comprising an aluminoxane compound may be prepared in which the aluminoxane is provided as a poly (hydrocarbuminium oxide), or in which aluminoxane is provided as the combination of an alkylaluminum compound and a source of active protons. such as water. Aluminoxanes may also be referred to as poly (hydrocarbuminium oxides) or organoaluminoxanes.

The other catalyst components can typically be contacted with the aluminoxane in a saturated hydrocarbon compound solvent, although any solvent that is substantially inert to the reactants, intermediates and products of the activation step can be used. The catalytic composition formed in this way can be collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition can be introduced into the polymerization reactor without being isolated.

The aluminoxane compound may be an oligomeric aluminum compound comprising linear structures, cyclic structures or structures in cages or mixtures of the three. Cyclic aluminoxane compounds that have the formula:

wherein R in this formula can independently be a linear or branched alkyl having 1 to 10 carbon atoms, and p in this formula can be an integer from 3 to 20, are encompassed by this invention. The AlRO moiety shown here may also constitute the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes that have the formula:

wherein each R in this formula can independently be a linear or branched alkyl having 1 to 10 carbon atoms and q in this formula can be an integer from 1 to 50, are encompassed by this invention.

In addition, aluminoxanes can have cage structures of the formula Rt5r + aRbr-aAl4fO3r, wherein each Rt can independently be a linear or branched terminal alkyl group having 1 to 10 carbon atoms; each Rb can independently be a linear or branched bridge alkyl group having 1 to 10 carbon atoms; r can be 3 or 4 can already be equal to hai (3) - no (2) no (4), where nAl (3) is the number of three coordinated aluminum atoms, no (2) is the number of two coordinated oxygen atoms and not (4) is the number of 4 coordinated oxygen atoms.

Thus, the aluminoxanes that can be used in the catalytic compositions can generally be represented by formulas such as (R-Al-O) p, R (R-Al-O) qAlR2 and the like. In these formulas, each R group can typically be a linear or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of aluminoxane compounds that can be used according to the present invention include methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, secbutylaluminoxane, iso-butylalumino-penoxumumino-penoxumumum-1-linoxyl-penoxyl-1-linoxyl-penoxyl-1-yl-linoxano-penoxyl-1-yl-lino-nano-lino-n-yl-lino-nano-lino-n-yl-lino-nano-lino-methoxy-lino-n-yl-lino-nano-lino-n-ylinoxanoxano compound , 3-pentylaluminoxane, isopentylaluminoxane, neopentyl aluminoxane, but not limited to these, and the like, or any combination thereof. Methylaluminoxane, ethylaluminoxane and iso-butylaluminoxane can be prepared from trimethylaluminum, triethylaluminum or triisobutylaluminum, respectively, and are sometimes referred to as poly (methyl aluminum oxide), poly (ethylaluminum oxide) and poly (isobutylaluminum oxide). Also within the scope of the invention is the use of an aluminoxane in combination with a trialkylaluminum, such as that described in US Pat. 4,794,096.

The present description contemplates many values of pyq in the formulas of aluminoxane (R-Al-O) p and R (R-Al-O) qAlR2, respectively. In some aspects, pyq may be at least 3. However, depending on how the organoaluminoxane is prepared, stored and used, the values of pyq may vary in a single aluminoxane sample and such organoaluminoxane combinations are contemplated herein. memory.

In the preparation of a catalytic composition containing an aluminoxane, the molar ratio of the total moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of metallocene complex (s) in the composition may generally be between about 1: 10 and about 100,000: 1. In another aspect, the molar ratio may be in the range of about 5: 1 to about 15,000: 1. Optionally, the aluminoxane may be added to a polymerization zone at intervals of about 0.01 mg / about 1000 mg / l, about 0.1 mg / about 100 mg / l about 1 mg / about 50 mg / l.

Organoaluminoxanes can be prepared by various procedures. Examples of organoaluminoxane preparations are described in US Patents Nos. 3,242,099 and 4,808,561. For example, water can be reacted in an inert organic solvent with an alkylaluminum compound, such as (RZ) 3Al, to form the desired organoaluminoxane compound. Although linking to the following statement is not intended, it is believed that this method of synthesis can provide a mixture of both linear and cyclic R-Al-O aluminoxane species, both encompassed by this invention. Alternatively, organoaluminoxane compounds can be prepared by reacting an alkylaluminum compound, such as (RZ) 3Al, with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.

Organoboro and organoborate compounds

According to another aspect, the catalytic composition may comprise an organoboro and organoborate compound. Such compounds may include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, fluoroorganoboro compounds and fluoroorganoborate compounds are contemplated.

Any fluororganoboro or fluoroorganoborate compound can be used with the present invention. Examples of fluoroorganoborate compounds that can be used in the present invention may include fluorinated aryl borates such as N, N-dimethylanilinium, tetrakis (pentafluorophenyl) triphenylcarbenium, tetrakis (pentafluorophenyl) tetrahydrate tetrakis (pentafluorophenyl) tetrahydrate N, N-dimethylanilinium [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, but not limited to these, and the like, or mixtures thereof. Examples of fluoroorganoboro compounds that can be used as cocatalysts in the present invention may include tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, but not limited to these, and the like, or mixtures thereof. . Although linking to the following theory is not intended, these examples of fluoroorganoborate and fluoroorganoboro compounds, and related compounds, can form "weakly coordinating" anions when combined with a transition metal complex (see, for example, US Pat. 5,919,983).

Applicants also contemplate the use of diboro compounds, or bis-boron, or other bifunctional compounds containing two or more boron atoms in the chemical structure, as described in J. Am. Chem. Soc., 2005, 127 , pp. 14756-14768.

Generally, any amount of organoboro compound can be used. According to one aspect, the molar ratio of the total moles of organoboro compound (or compounds) or organoborate to the total moles of metallocene compounds in the catalytic composition may be in the range of about 0.1: 1 to about 15: 1 Typically, the amount of the fluoroorganoboro or fluoroorganoborate compound used may be from about 0.5 moles to about 10 moles of boron / borate compound per mole of metallocene complexes. According to another aspect of this invention, the amount of the fluoroorganoboro or fluoroorganoborate compound may be from about 0.8 moles to about 5 moles of boron / borate compound per mole of metallocene complexes.

Ionizing ionic compounds

In another aspect, the catalyst compositions described herein may comprise an ionizing ionic compound. An ionizing ionic compound is an ionic compound that can function as a cocatalyst to increase the activity of the catalytic composition. Although linkage to the theory is not intended, it is believed that the ionizing ionic compound may be able to react with a metallocene complex and convert the metallocene complex into one or more cationic metallocene complexes or incipient cationic metallocene complexes. Again, although linkage to the theory is not intended, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, such as a monoanionic X ligand, from the metallocene complex. However, the ionizing ionic compound can be a cocatalyst regardless of whether it ionizes the metallocene compound, subtracts an X ligand so that an ionic pair is formed, weakens the metal-X bond in the metallocene, simply coordinates to a ligand X or activates metallocene by some other mechanism.

In addition, it is not necessary for the ionizing ionic compound to activate the metallocene compound only. The activation function of the ionizing ionic compound may be evident in the increased activity of the catalytic composition as a whole, compared to a catalytic composition that does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds may include the following compounds: tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) ammonium tetrakis (m-tolyl) borate, tetrakis (2,4- tri (n-butyl) ammonium dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] tri (n-) tetrakis (pentafluorophenyl) borate butyl) ammonium, N, N-dimethylanilinium tetrakis (p-tolyl) borate, N, N-dimethylanilinium tetrakis (N-N-dimethylphenyl) tetrakis, N, N-dimethylanilinium tetrarate, tetrakis ( N, N-dimethylanilinium, tetrakis [3,5-bis (trifluoromethyl) phenyl] N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium, tetrakis (p-) 3,5-dimethylphenyl) borate tolyl) triphenylcarbenium borate, tetrakis (m-tolyl) triphenylcarbenium borate, tetrakis (2,4-dimethylphenyl) triphenylcarbenium borate, tetrakis (3,5-dimethylphenyl) triphenylcarbenium borate, tetrakis [3,5-bis (tripheluoromethyl) phenyl] triphenylcarbenium borate, tetrakis (pentafluorophenyl) triphenylcarbenium borate, tetrakis (p-tolyl) borate detropyllium, tetrakis (m-tolyl) borate detropyllium, tetrakis (2,4-dimethylphenyl) borate detropylyl, tetrakis (3,5-dimethylphenyl ) tropilio borate, tet Taryl rakis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) tropyl borate, tetrakis (pentafluorophenyl) tropium borate, tetrakis (pentafluorophenyl) lithium borate, lithium tetraphenylborate, p-tolyl) (p-tolyl) lithium borate, tetrakis (m-tolyl) lithium borate, tetrakis (2,4-dimethylphenyl) lithium borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl) borate, sodium tetraphenylborate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate, tetrafluoroborate sodium, tetrakis (pentafluorophenyl) potassium borate, potassium tetraphenylborate, tetrakis (p-tolyl) potassium borate, tetrakis (m-tolyl) potassium borate, tetrakis (2,4-dimethylphenyl) potassium borate, tetrakis (3, 5-dimethylphenyl) potassium borate, potassium tetrafluoroborate, lithium tetrakis (pentafluorophenyl) aluminate, lithium tetraphenylaluminate, tetrak lithium is (p-tolyl) aluminate, lithium tetrakis (m-tolyl) lithium tetrakis, lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis (3,5-dimethylphenyl) aluminate, lithium tetrafluoroaluminate, tetrakis ( sodium pentafluorophenyl) aluminate, sodium tetraphenylaluminate, sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethylphenyl) aluminate, tetrakis (3,5-dimethylphenyl) sodium aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) potassium aluminate, potassium tetraphenylaluminate, tetrakis (p-tolyl) potassium aluminate, tetrakis (m-tolyl) potassium aluminate, tetrakis (2,4-dimethylphenyl) aluminate potassium, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate, and the like, or combinations thereof. The ionizing ionic compounds useful in this invention are not limited thereto; Other examples of ionizing ionic compounds are described in US Pat. Nos. 5,576,259 and 5,807,938.

Organocinc, organomagnesium and organolithium compounds

Other aspects relate to catalytic compositions that may include an organocinc compound, an organomagensium compound, an organolithium compound, or a combination thereof. In some aspects, these compounds have the following general formulas:

Zn (X10) (X11);

Mg (X12) (X13)

Y

Li (X ¹⁴ ).

In these formulas, X ¹⁰ , X ¹² and X ¹⁴ can independently be a C1 to C18 hydrocarbyl group and X ¹¹ and X ¹³ can independently be H, a halide or a C1 to C18 hydrocarbyl group or a C1 to C18 hydrocarboxy group. It is assumed that X ¹⁰ and X ¹¹ (or X ¹² and X ¹³ ) may be the same or that X ¹⁰ and X ¹¹ (or X ¹² and X ¹³ ) may be different.

In one aspect, X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ can independently be any C1 to C18 hydrocarbyl group, C1 to C12 hydrocarbyl group, C1 to C ⁸ hydrocarbyl group or C1 to C5 hydrocarbyl group, described in present memory In another aspect, X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ can independently be any C1 to C18 alkyl group, C2 to C18 alkenyl group, C ⁶ to C18 aryl group or C7 to C18 aralkyl group described herein. memory; alternatively, any alkyl group of C1 to C12, C2 to C12 alkenyl group, aryl group or C ⁶ to C12 aralkyl group C7 through C12 described herein; or alternatively, any alkyl group C1 to C5, C2 to C5 alkenyl group, aryl group or C ⁶ to Ce Ce C7 aralkyl group described herein. Thus, X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group , a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group , a heptadecenyl group, an octadecenyl group, a phenyl group, a naphthyl group, a benzyl group or a tolyl group, and the like. In yet another aspect, X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ can independently be methyl, ethyl, propyl, butyl or pentyl (eg, neopentyl), or both X ¹⁰ and X ¹¹ (or both X ¹² as X ¹³ ) they can be methyl, or ethyl, or propyl, or butyl, or pentyl (eg, neopentyl).

X ¹¹ and X ¹³ can independently be H, a halide or a C1 to C18 hydrocarbyl group or C1 to C18 hydrocarboxy group (for example, any C1 to C18 hydrocarboxy group, C1 to C12, C1 to C10 or C1 to Ce described in present memory). In some aspects, X ¹¹ and X ¹³ may independently be H, a halide (eg, Cl) or a C1 to C18 hydrocarbyl group or a C1 to C18 hydrocarboxy group; alternatively, H, a halide or a C1 to Ce hydrocarbyl group or a C1 to Ce hydrocarboxy group; or alternatively, H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl (eg, neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl , octenyl, nonenyl, Decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy, xyloxy or benzoxy.

In other aspects, the organocinc compound and / or the organomagnesium compound may have one or two hydrocarbylsilyl moieties. Each hydrocarbyl of the hydrocarbylsilyl group may be any hydrocarbyl group described herein (for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C6 to C18 aryl group, a C7 to C18 aralkyl group, etc.). Non-limiting illustrative examples of hydrocarbylsilyl groups may include trimethylsilyl, triethylsilyl, tripropylsilyl (eg, triisopropylsilyl), tributyl silyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, trimethylsilylmethyl, and the like, but not limited thereto.

Exemplary organocinc compounds that can be used as cocatalysts may include dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, dineopentyl zinc, di (trimethylsilyl) zinc, di (triethylsilyl) zinc, di (triisopropyl-alkyl) zinc, di (triphenylsilyl) zinc, di (allyl dimethyl) , di (trimethylsilylmethyl) zinc, and the like, or combinations thereof, but not limited to these.

Similarly, exemplary organomagnesium compounds may include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dyneopentyl magnesium, di (trimethylsilylmethyl) magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium magnesium chloride, butylmagnesium magnesium chloride , methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, propylmagnesium iodide, and magnesium magnesium iodide of methylmagnesium, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methylmagnesium proproxide, ethylmagnesium proproxide, butyl magnesium propylene oxide, propylene oxide Nesio, Neopentylmagnesium Propoxide, Trimethylsilylmethylmagnesium Propoxide, Methylmagnesium Phenoxide, Ethylmagnesium Phenoxide, Propylmagnesium Phenoxide, Butylmagnesium Phenoxide, Neopentylmagnesium Phenoxide, Trimethylsilyl Phenylo, or Similar Combinations to these combinations of these combinations

Likewise, exemplary organolithium compounds may include methyl lithium, ethyl lithium, propylthio, butyl lithium (for example, t-butyl lithium), neopentyl lithium, trimethylsilyl methyl methyl, phenylithio, tolylithio, xylyl lithium, benzylithium, (dimethylphenyl) methyl lithium, and such combinations, alilithium, these combinations , but not limited to these.

Olefinic monomers

Unsaturated reactants that can be employed with catalytic compositions and the polymerization processes of this description can typically include olefinic compounds having 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention encompasses homopolymerization processes using a single olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization reactions, etc., using an olefinic monomer with at least one different olefinic compound. For example, the resulting copolymers, terpolymers, etc., of ethylene may generally contain a majority amount of ethylene (> 50 mole percent) and a minor amount of comonomer (<50 mole percent), although this is not a request. Comonomers that can be copolymerized with ethylene can often have 3 to 20 carbon atoms in their molecular chain.

In this invention, acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention may include ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, all four normal octenes (eg 1-octene), the four normal nonenos, the five normal deans, and the like, or mixtures of two or more of these compounds, but not limited to these. Cyclic and bicyclic olefins including cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, but not limited to these, can also be polymerized as described above. In the present invention, styrene can also be used as a monomer. In one aspect, the olefinic monomer may comprise a C2-C10 olefin; alternatively, the olefinic monomer may comprise ethylene or alternatively, the olefinic monomer may comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinic monomer may comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. According to one aspect of this invention, the olefinic monomer in the polymerization process may comprise ethylene. In this aspect, examples of suitable olefinic comonomers may include propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl -1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, or combinations thereof , but not limited to these. In accordance with one aspect of the present invention, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene or any combination thereof; or alternatively, 1-butene, 1-hexene, 1-octene, or any combination of these.

In general, the amount of comonomer introduced into an area of the reactor to produce a copolymer can be from about 0.01 to about 50 percent by weight of the comonomer based on the total weight of the monomer and the comonomer. According to another aspect of the present invention, the amount of comonomer introduced in a zone of the reactor it can be from about 0.01 to about 40 percent by weight of comonomer based on the total weight of the monomer and the comonomer. In yet another aspect, the amount of comonomer introduced into an area of the reactor may be from about 0.1 to about 35 percent by weight of the comonomer based on the total weight of the monomer and the comonomer. In yet another aspect, the amount of comonomer introduced into an area of the reactor may be from about 0.5 to about 20 percent by weight of comonomer based on the total weight of the monomer and the comonomer.

While the limitation is not intended by this theory, it is believed that when branched, substituted or functionalized olefins are used as reactants, a steric hindrance can prevent and / or slow the polymerization process. Thus, the branched and / or cyclic portions of the olefin without some carbon-carbon double bond would not be expected to prevent the reaction in the way that the same olefin substituents located closest to the carbon-carbon double bond would. According to one aspect of the present invention, at least one monomer / reactant can be ethylene, so that the polymerizations are either a homopolymerization involving only ethylene or copolymerizations with an acyclic, cyclic, terminal, internal, linear, branched olefin , substituted or unsubstituted different. In addition, the catalyst compositions of this invention can be used in the polymerization of diolefin compounds that include 1,3-butadiene, isoprene, 1,4-pentadiene and 1,5-hexadiene, but not limited to these.

Catalytic compositions

In some aspects, the present description employs catalytic compositions containing catalyst component I, catalyst component II, catalyst component III and an activator (one or more than one). These catalytic compositions can be used to produce polyolefins - homopolymers, copolymers, and the like - for a variety of end-use applications. Catalytic components I, II and III were discussed herein above. In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one catalyst component metallocene compound I and / or more than one catalyst component metallocene compound II and / or more than one catalyst component metallocene compound III. In addition, additional catalyst compounds - other than those specified as catalyst component I, II and III - may be employed in the catalyst compositions and / or polymerization processes, provided that the additional catalyst compounds do not impair the advantages described herein. Additionally, more than one activator can also be used.

The metallocene compounds of catalytic component I were discussed above. For example, in some aspects, the catalytic component I may comprise (or consist essentially of, or consist of) a metallocene compound without bridges of formula (A). Metallocene compounds with catalytic component II bridges were also discussed above. For example, in some aspects, the catalytic component II may comprise (or consist essentially of, or consist of) a metallocene compound with the formula (B). In addition, metallocene compounds with catalytic component III bridges were discussed above. For example, in some aspects, catalyst component III may comprise (or consist essentially of, or consist of) a metallocene compound with the formula (C).

Generally, the catalyst compositions comprise catalyst component I, catalyst component II, catalyst component III and an activator. In aspects of the invention, the activator may comprise an activating support (for example, an activating support comprising a solid oxide treated with an electron acceptor anion). The activating supports useful in the present invention were discussed above. Optionally, said catalyst compositions may further comprise one or more of a cocatalyst compound (suitable cocatalysts, such as organoaluminum compounds, also discussed above). Thus, a catalytic composition of this invention may comprise catalytic component I, catalyst component II, catalyst component III, an activating support and an organoaluminum compound. For example, the activating support may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphate silica, and the like, or combinations thereof . Additionally, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, hydride. diisobutylaluminum, diethyl aluminum ethoxide, diethyl aluminum chloride, and the like, or combinations thereof. Accordingly, a catalytic composition consistent with aspects of the invention may comprise (or consist essentially of, or consist of) a metallocene compound based on zirconium or hafnium without bridges; a zirconium-based metallocene compound with bridges with a fluorenyl group, and without aryl groups in the bridge group; a zirconium or hafnium-based metallocene compound with bridges with a fluorenyl group, and an aryl group in the bridge group; sulfated alumina (or fluorinated silica-alumina, or alumina coated with fluorinated silica); and triethylaluminum (or triisobutylaluminum).

In another aspect, a catalytic composition is provided comprising catalytic component I, catalytic component II, catalytic component III, an activating support and an organoaluminum compound, wherein this catalytic composition is substantially free of aluminoxanes, organoboro or organoborate compounds, compounds ionizing ionics and / or other similar materials; alternatively, it is substantially free of aluminoxanes; alternatively, it is substantially free of organoboro or organoborate compounds; or alternatively, it is substantially free of ionizing ionic compounds. In these aspects, the catalytic composition has catalytic activity, which will be discussed below, in the absence of these additional materials. For example, a catalytic composition of the present invention can consist essentially of a catalytic component I, catalytic component II, catalytic component III, an activating support and an organoaluminum compound, where there are no other materials in the catalytic composition that increase or decrease the activity of the catalytic composition by more than about 10% of the catalytic activity of the catalytic composition in the absence of said materials.

However, in other aspects, these activators / cocatalysts can be used. For example, a catalyst composition comprising catalyst component I, catalyst component II, catalyst component III, and an activating support may further comprise an optional cocatalyst. Suitable cocatalysts in this aspect may include aluminoxane compounds, organoboro or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organocinc compounds, organomagnesium compounds, organolithium compounds, and the like, or any combination thereof; or alternatively, organoaluminum compounds, organocinc compounds, organomagnesium compounds, organolithium compounds or any combination thereof, but not limited to these. There may be more than one cocatalyst in the catalytic composition.

In a different aspect, a catalytic composition is provided that does not require an activating support. Said catalytic composition may comprise catalytic component I, catalytic component II, catalytic component III, and an activator, wherein the activator comprises an aluminoxane compound, an organoboro or organoborate compound, an ionizing ionic compound, or combinations thereof.

In a particular aspect contemplated herein, the catalyst composition is a catalytic composition comprising an activator (one or more than one), only a metallocene compound catalytic component I, only a metallocene compound catalytic component II and only one compound of metallocene catalyst component III. In these and other aspects, the catalyst composition may comprise an activator (for example, an activating support comprising a solid oxide treated with an electron acceptor anion); only a metallocene compound based on zirconium or hafnium without bridges or dinuclear metallocene compound based on zirconium and / or hafnium without bridges; only a zirconium-based metallocene compound with bridges with a fluorenyl group, and without aryl groups in the bridge group; and only a metallocene compound based on zirconium or hafnium with bridges with a fluorenyl group, and an aryl group in the bridge group.

This description further encompasses methods for preparing these catalyst compositions, such as, for example, by contacting the respective catalyst components in any order or sequence.

Catalytic component I, catalytic component II or catalytic component III, or any combination thereof, can be previously contacted with an olefinic monomer if desired, the olefinic monomer, and an organoaluminum compound does not necessarily have to be polymerized during a first period of time before contacting this previously contacted mixture with an activating support. The first period of contact time, the precontact time, between the metallocene compound or compounds, the olefinic monomer and the organoaluminum compound typically ranges from a period of time from about 1 minute to about 24 hours, for example, from about 3 minutes to about 1 hour. Precontact times of about 10 minutes to about 30 minutes can also be used. Alternatively, the precontact process can be carried out in multiple stages, rather than in a single stage, in which multiple mixtures can be prepared, each comprising a different set of catalytic components. For example, at least two catalyst components can be contacted forming a first mixture, followed by bringing the first mixture into contact with at least one other catalyst component forming a second mixture, etc.

Multiple stages of precontact can be carried out in a single container or in multiple containers. In addition, multiple precontact stages can be performed in series (sequentially), in parallel, or a combination of these. For example, a first mixture of two catalytic components can be formed in a first container, a second mixture comprising the first mixture plus an additional catalytic component can be formed in the first container or in a second container, which is typically placed downstream of the first container.

In another aspect, one or more of the catalytic components can be divided and used in different precontact treatments. For example, part of a catalytic component can be fed to a first precontact container for contacting it with at least one other catalytic component, while the rest of that same catalytic component can be fed to a second precontact container for prior contact. with at least one other catalytic component, or it can be fed directly to the reactor, or a combination of these. The precontact can be carried out in any suitable equipment, such as tanks, mixing tanks with stirring, various static mixing devices, a flask, a container of any type, or combinations of these devices.

In another aspect, the various catalyst components (for example, a metallocene catalyst component I, II and / or III, an activating support, an organoaluminum cocatalyst and optionally an unsaturated hydrocarbon) can be contacted in the polymerization reactor simultaneously at the same time. that the reaction of polymerization. Alternatively, two or more of these catalyst components may be previously contacted in a vessel prior to entering the reaction zone. This precontacting step can be continuous, in which the previously contacted product can be continuously fed to the reactor, or it can be a stepwise or batch process in which a batch of product previously contacted can be added to prepare a catalytic composition. . This precontact stage can be carried out for a period of time that can vary from a few seconds to as many as several days, or more. In this aspect, the continuous precontact step can generally last from about 1 second to about 1 hour. In another aspect, the continuous precontact step may last from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the previously contacted mixture of catalyst component I and / or catalyst component II and / or catalyst component III, the olefinic monomer and the organoaluminum cocatalyst are contacted with the activating support, this composition (with the addition of activating support) may be called the "mixture subsequently contacted". The subsequently contacted mixture may optionally remain in contact for a second period of time, the post-contact time, prior to the start of the polymerization process. Post-contact times between the previously contacted mixture and the activator support generally range from about 1 minute to about 24 hours. In another aspect, the postcontact time may be in a range of about 3 minutes to about 1 hour. The precontact stage, the postcontact stage, or both, can increase the productivity of the polymer when compared to the same catalytic composition that is prepared without precontact or postcontact. However, neither a precontact stage nor a postcontact stage is required.

The subsequently contacted mixture may be heated at a temperature and for a period of time sufficient to allow adsorption, impregnation or interaction of the previously contacted mixture and the activating support, so that a portion of the components of the mixture Previously contacted can be immobilized, adsorbed or deposited therein. When heating is used, the subsequently contacted mixture can generally be heated at a temperature in the range between about 0 ° F and about 150 ° F or between about 40 ° F and about 95 ° F.

According to one aspect, the weight percentage of catalyst component I may be in a range of about 5% to about 80%, the weight percentage of catalyst component II may be in a range of about 5% to about 80% and The percentage by weight of catalytic component III may be in a range of about 5% to about 80%. These weight percentages are based on the total weight of catalyst components I, II, and III that equal 100% and does not include other components of the catalyst composition, for example, activator, cocatalyst, etc. In another aspect, the catalyst composition may contain from about 20% to about 50% by weight of catalyst component I, from about 5% to about 30%, by weight, of catalyst component II and from about 20% to about 50%, by weight, of catalyst component III (as before, the weight percentage is based on the total weight of catalyst components I, II, and III that equal 100%). In yet another aspect, the catalyst composition may contain from about 25% to about 45%, by weight, of catalyst component I, from about 5% to about 30%, by weight, of catalyst component II and from about 25% to about 45%, by weight, of catalyst component III. In these and other aspects, the weight percentage of catalytic component II may be in a range of from about 5% to about 25%, from about 5% to about 20% or from about 10% to about 25%. Also, the weight ratio of catalyst component I to catalyst component III, in some aspects, may be in a range of about 10: 1 to about 1: 10; from about 8: 1 to about 1: 8; from about 5: 1 to about 1: 5; from about 4: 1 to about 1: 4; from about 3: 1 to about 1: 3; from about 2: 1 to about 1: 2; from about 1.5: 1 to about 1: 1.5; from about 1.25: 1 to about 1: 1.25 or from about 1.1: 1 to about 1: 1.1.

When a precontact step is used, the molar ratio of the total moles of olefinic monomer to the total moles of metallocene (s) in the previously contacted mixture may typically be in a range of about 1: 10 to about 100,000: 1. The total moles of each component are used in this relationship to explain aspects of this invention where more than one olefinic monomer and / or more than one metallocene compound is used in a precontact step. In addition, this molar ratio may be in a range of about 10: 1 to about 1000: 1 in another aspect of the invention.

Generally, the weight ratio of the organoaluminum compound to the activating support may be in a range of about 10: 1 to about 1: 1000. If more than one organoaluminum compound and / or more than one activating support is used, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of the organoaluminum compound to the activating support may be in a range of from about 3: 1 to about 1: 100 or from about 1: 1 to about 1: 50.

In some aspects of this invention, the weight ratio of metallocene compounds (total of catalyst component I, II and III) to activating support may be in a range of from about 1: 1 to about 1: 1 000 000. If used More than one activating support, this ratio is based on the total weight of the activating support. In another aspect, this weight ratio may be in a range of from about 1: 5 to about 1: 100,000 or from about 1: 10 to about 1: 10,000. In another aspect, the weight ratio of the metallocene compounds The activator support may be in a range of about 1: 20 to about 1: 1000.

The catalyst compositions of the present invention generally have a catalytic activity greater than about 100 grams of polyethylene (homopolymer, copolymer, etc., as the context requires) per gram of activating support per hour (abbreviated g / g / h). In another aspect, the catalytic activity may be greater than about 150 g / g / h, greater than about 250 g / g / h or greater than about 500 g / g / h. In yet another aspect, the catalyst compositions of this invention can be characterized in that they have a catalytic activity greater than about 550 g / g / h, greater than about 650 g / g / h or greater than about 750 g / g / h. In yet another aspect, the catalytic activity may be greater than about 1000 g / g / h, greater than about 1500 g / g / h or greater than about 2000 g / g / h. These activities are measured under suspension polymerization conditions using isobutane as a diluent, at a polymerization temperature of approximately 95 ° C and a reactor pressure of approximately 3 Mpa (420 psig). In addition, said catalytic activities can be achieved when the catalyst composition contains a cocatalyst, such as an organoaluminum compound (eg, triethylaluminum, triisobutylaluminum, etc.). Additionally, in some aspects, the activating support may comprise sulfated alumina, fluorinated silica-alumina or alumina coated with fluorinated silica, although it is not limited thereto.

As discussed above, any combination of catalyst component I, catalyst component II, catalyst component III, activating support, organoaluminum compound and the olefinic monomer, can be previously contacted in some aspects of this invention. When any previous contact with olefinic monomer occurs, it is not necessary that the olefinic monomer used in the precontact step be the same as the olefin to be polymerized. In addition, when a precontact stage is used between any combination of the catalytic components for a first period of time, this previously contacted mixture can be used in a postcontact stage below between any other combination of catalytic components during a second period of weather. For example, one or more metallocene compounds, the organoaluminum compound and 1-hexene compound may be used in a precontacting stage for a first period of time and this previously contacted mixture can then be contacted with the activating support to form a Subsequently contacted mixture which can be contacted for a second period of time prior to the start of the polymerization reaction. For example, the first period of contact time, the precontact time, between any combination of the metallocene compound or compounds, the olefinic monomer, the activating support and the organoaluminum compound can be from about 1 minute to about 24 hours, from about 3 minutes to about 1 hour or from about 10 minutes to about 30 minutes. The subsequently contacted mixture may optionally be allowed to remain in contact for a second period of time, the subsequent contact time, before the polymerization process is initiated. According to one aspect of this invention, the subsequent contact times between the previously contacted mixture and any remaining catalyst component can be from about 1 minute to about 24 hours or from about 5 minutes to about 1 hour.

Polymerization procedures

The catalytic compositions of the present description can be used to polymerize olefins in order to form homopolymers, copolymers, terpolymers and the like. One such method for polymerizing olefins in the presence of a catalytic composition of the present disclosure may comprise bringing the catalytic composition into contact with an olefin monomer and, optionally, an olefin comonomer (one or more) under polymerization conditions to produce a polymerization. olefinic polymer, wherein the catalyst composition may comprise catalyst component I, catalyst component II, catalyst component III, an activator and an optional cocatalyst. The catalytic components I, II and III were discussed above. For example, a catalyst component I can comprise a metallocene compound without bridges with the formula (A), a catalyst component II can comprise a metallocene compound with bridges with the formula (B) and the catalyst component III can comprise a compound of metallocene with bridges with the formula (C).

According to one aspect, the polymerization process may employ a catalyst composition comprising catalyst component I, catalyst component II, catalyst component III, and an activator, wherein the activator comprises an activating support. Activating supports useful in polymerization processes were discussed above. The catalytic composition, optionally, may further comprise one or more of an organoaluminum compound (or other suitable cocatalyst). Thus, a process for polymerizing olefins in the presence of a catalytic composition may employ a catalytic composition comprising catalyst component I, catalyst component II, catalyst component III, an activating support and an organoaluminum compound. In some aspects, the activating support may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica alumina, silica-sulfated alumina, silica - fluorinated zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphate silica, and the like, or combinations thereof. In some aspects, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethyl aluminum ethoxide, diethylaluminum chloride and the like, or combinations thereof.

According to another aspect, the polymerization process can employ a catalytic composition comprising catalyst component I, catalyst component II, catalyst component III, an activating support and an optional cocatalyst, wherein the cocatalyst can comprise an aluminoxane compound, an organoboro compound or organoborate, an ionizing ionic compound, an organoaluminum compound, an organocinc compound, an organomagnesium compound, or an organolithium compound, or any combination thereof. Therefore, the aspects relate to a process for polymerizing olefins in the presence of a catalytic composition, the methods comprising contacting a catalytic composition with an olefinic monomer and optionally an olefinic (one or more) comonomer under polymerization conditions to produce an olefinic polymer and the catalyst composition may comprise catalytic I, catalyst component II, catalyst component III, an activating support and an aluminoxane compound; alternatively, catalytic component I, catalytic component II, catalytic component III, an activating support and an organoboro or organoborate compound; alternatively, catalytic component I, catalytic component II catalytic component III, an activating support and an ionizing ionic compound; alternatively, catalytic component I, catalytic component II catalytic component III, an activating support and an organoaluminum compound; alternatively, catalytic component I, catalytic component II catalytic component III, an activating support and an organocinc compound; alternatively, catalytic component I, catalytic component II, catalytic component III, an activating support and an organomagnesium compound; or alternatively, catalytic component I, catalytic component II, catalytic component III, an activating support and an organolithium compound. Also, more than one cocatalyst can be employed, for example, an organoaluminum compound and an aluminoxane compound, an organoaluminum compound and an ionizing ionic compound, etc.

According to another aspect, the polymerization process can employ a catalytic composition comprising only a catalyst component metallocene compound I, only a catalyst component metallocene compound II, only a catalyst component metallocene compound III, an activating support and an organoaluminum compound .

According to another aspect, the polymerization process can employ a catalyst composition comprising catalyst component I, catalyst component II, catalyst component III, and an activator, wherein the activator comprises an aluminoxane compound, an organoboro or organoborate compound, a compound ionic ionic, or combinations thereof.

Catalytic compositions are provided for any olefin polymerization method that uses various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor that can polymerize olefin monomers and comonomers (one or more of a comonomer) to produce homopolymers, copolymers, terpolymers and the like. The various types of reactors include those that can be referred to as a batch reactor, suspension reactor, gas phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor and the like or combinations thereof. Suitable polymerization conditions are used for the various types of reactor. The gas phase reactors may comprise fluidized bed reactors or stepped horizontal reactors. Suspension reactors may comprise vertical or horizontal loops. High pressure reactors may comprise tubular reactors or autoclaves. Reactor types may include batch or continuous procedures. Continuous procedures could use intermittent or continuous product discharge. The processes may also include total or partial direct recycling of unreacted monomers, unreacted comonomer and / or diluent.

The polymerization reactor systems of the present description may comprise one type of reactor in a system or multiple reactors of the same or different type. The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device, which makes it possible to transfer the polymers produced in the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may differ from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include manual transfer of the polymer from one reactor to subsequent reactors for continued polymerization. Multiple reactor systems may include any combination that includes multiple loop reactors, multiple gas phase reactors, a combination of gas phase and loop reactors, multiple high pressure reactors or a combination of high pressure reactors with loop and / or gas phase, but not limited to these. Multiple reactors can operate in series, in parallel or both.

According to one aspect, the polymerization reactor system may comprise at least one loop suspension reactor comprising vertical or horizontal loops. When polymerization occurs, monomers, diluents, catalysts and comonomers can be fed continuously to a loop reactor. Generally, continuous processes may comprise the continuous introduction of a monomer / comonomer, a catalyst and a diluent in a polymerization reactor and the continuous removal of this reactor from a suspension comprising polymer particles and the diluent. The reactor effluent can be subjected to instantaneous vaporization to remove the solid polymer from liquids comprising the diluent, monomer and / or comonomer.

Various technologies may be employed at this stage of separation that include instantaneous vaporization that may include any combination of heat addition and pressure reduction, separation by cyclonic action in either a cyclonic or hydrocyclonic separator or separation by centrifugation, but not limited to these.

A typical suspension polymerization process (also known as the particle formation process) is described, for example, in US Pat. Nos. 3,248,179; 4,501,885; 5,565,175; 5,575,979; 6,239,235; 6,262,191 and 6,833,415.

Suitable diluents used in suspension polymerization include the monomer that is being polymerized and hydrocarbons that are liquid under the conditions of the reaction, but not limited to these. Examples of suitable diluents include hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane, but not limited to these. Some loop polymerization reactions may occur in bulk conditions in which no diluent is used. An example is the polymerization of propylene monomer as described in US Patent No. 5,455,314.

According to another aspect, the polymerization reactor may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more monomers that are continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream can be removed from the fluidized bed and recycled to the reactor. Simultaneously, the polymer product can be removed from the reactor and a new unprocessed monomer or monomer can be added to replace the polymerized monomer. Such gas phase reactors may comprise a multi-stage gas phase polymerization process of olefins in which the olefins are polymerized in the gas phase in at least two independent gas phase polymerization zones, by feeding a polymer containing catalyst formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is described in US Patent Nos. 5,352,749, 4,588,790 and 5,436,304.

According to another aspect, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have several zones in which unprocessed catalysts, initiators or monomers are added. An inert gas stream can drag the monomer and introduce it into an area of the reactor. A gas stream can drag initiators, catalysts and / or catalytic components and introduce them into another area of the reactor. Gas streams can be mixed in the polymerization. Heat and pressure can be used suitably to obtain optimal polymerization reaction conditions.

According to yet another aspect, the polymerization reactor may comprise a solution polymerization reactor where the monomer / comonomer is contacted with the catalytic composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer can be used. If desired, the monomer / comonomer can be contacted with the product of the catalytic reaction in the vapor phase in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Stirring can be used to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of the polymerization.

Polymerization reactors suitable for the present disclosure may additionally comprise any combination of at least one feed system of unprocessed material, at least one catalyst feed system or catalytic components, and / or at least one polymer recovery system. Additionally, the reactor systems suitable for the present invention may comprise systems for purification of raw material, preparation and storage of catalysts, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis and control of procedures

The polymerization conditions that are controlled to determine efficacy and provide the polymer with the desired properties may include temperature, pressure and the concentrations of various reactants. The polymerization temperature can affect the catalytic productivity, the molecular weight of the polymer and the molecular weight distribution. According to the Gibbs free energy equation, any temperature below the depolymerization temperature can be a suitable polymerization temperature. Typically, this includes from about 60 ° C to about 280 ° C, for example, or from about 60 ° C to about 120 ° C, depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature can generally be within a range of about 70 ° C to about 100 ° C, or about 75 ° C to about 95 ° C.

Suitable pressures will also vary according to the type of reactor and polymerization. Typically, the pressure for liquid phase polymerizations in a loop reactor is less than 1000 psig (6.9 MPa). The pressure for gas phase polymerization is normally about 200 psig to 500 psig (1.4 MPa to 3.4 MPa). Generally, high pressure polymerization in tubular or autoclave reactors is performed at approximately 20,000 psig at 75,000 psig (from 138 MPa to 517 MPa). Polymerization reactors can also operate in a supercritical region that generally occurs at higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages.

Aspects of this description relate to olefin polymerization processes comprising bringing a catalytic composition into contact with an olefinic monomer and an olefinic comonomer under polymerization conditions to produce an olefinic polymer. The olefinic polymer (for example, an ethylene copolymer) produced by the process has a melt index in a range of about 0.005 g / 10 minutes to about 10 g / 10 minutes, an IFAC / IF ratio (melt index of high load / melt index) in a range of about 50 to about 500, a density in a range of about 0.915 g / cm 3 to about 0.965 g / cm 3, a non-bimodal molecular weight distribution and a reverse comonomer distribution.

Aspects of this description also refer to olefin polymerization processes that are carried out in the absence of added hydrogen. A process for polymerizing olefins may comprise bringing the catalyst composition into contact with an olefinic monomer and, optionally, an olefinic comonomer under polymerization conditions to produce an olefinic polymer, wherein the catalyst composition may comprise catalyst component I, catalyst component II, component catalytic III, an activator and an optional cocatalyst, wherein the polymerization process is carried out in the absence of added hydrogen. As one skilled in the art would recognize, hydrogen can be generated in situ by catalytic metallocene compositions in various olefin polymerization processes and the amount generated may vary depending on the catalytic composition and the specific metallocene compounds employed, the type of the polymerization process used, the polymerization reaction conditions used, etc.

In other aspects, it may be desirable to carry out the polymerization process in the presence of a certain amount of hydrogen added. Accordingly, a process for polymerizing olefins may comprise bringing the catalyst composition into contact with an olefinic monomer and, optionally, an olefinic comonomer under polymerization conditions to produce an olefinic polymer, wherein the catalyst composition comprises catalyst component I, component Catalytic II, Catalytic Component III, an activator and an optional cocatalyst, wherein the polymerization process is carried out in the presence of added hydrogen. For example, the ratio of hydrogen to olefinic monomer in the polymerization process can be controlled, often by the ratio of hydrogen feed to the olefinic monomer entering the reactor. The ratio of hydrogen added to olefinic monomer in the process can be controlled in a weight ratio ranging from about 25 ppm to about 1500 ppm, from about 50 ppm to about 1000 ppm or from about 100 ppm to about 750 ppm.

In some aspects, the ratio of hydrogen feed or reactant to the olefinic monomer can be kept substantially constant during the polymerization that is performed for a particular polymer grade. That is, the hydrogen: olefinic monomer ratio can be selected in a particular ratio in a range of about 5 ppm to about 1000 ppm or the like, and can be maintained in a ratio of about / -25% while polymerization is taking place. For example, if the target ratio is 100 ppm, then maintaining the hydrogen: olefinic monomer ratio substantially constant would mean maintaining the feed ratio between about 75 ppm and about 125 ppm. In addition, the addition of comonomer (or comonomers) can be substantially constant, and generally is, while polymerization is performed for a particular polymer grade.

However, in other aspects, it is contemplated that a monomer, comonomer (or comonomers) and / or hydrogen may be periodically pulsed to the reactor, for example, in a manner similar to that used in US Patent No. 5,739,220 and U.S. Patent Publication No. 2004/0059070.

The concentration of the reactants entering the polymerization reactor can be controlled to produce resins with certain physical and mechanical properties. The proposed end-use product that will be formed by the polymeric resin and the method of formation of that product can ultimately determine the desired polymer properties and attributes. Mechanical properties include stress, flexion, impact, creep, stress relaxation and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, fracture growth, long chain branching and rheological measurements.

This invention relates to polymers produced by any of the polymerization processes described herein and encompasses them. The articles of manufacture can be formed from the polymers produced according to this invention and / or can comprise them.

Polymers and articles

The olefinic polymers encompassed herein may include any polymer produced from any olefinic monomer and comonomer described herein. For example, the olefinic polymer may comprise an ethylene copolymer (for example, ethylene / a-olefin, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, etc.), a propylene copolymer, a ethylene terpolymer, a propylene terpolymer and the like, including combinations thereof. In one aspect, the olefinic polymer may be an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer or an ethylene / 1-octene copolymer, while in another aspect, the polymer Olefinic may be an ethylene / 1-hexene copolymer.

If the resulting polymer produced according to the present invention is, for example, an ethylene polymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. The articles of manufacture may be formed from the ethylene polymers of this invention, whose typical properties are provided below, and / or may comprise them.

Ethylene polymers (copolymers, terpolymers, etc.) produced according to some aspects of this invention can generally have a melt index (IF) of about 0.005 to about 10 g / 10 min. Melt indexes in the range of 0.005 g to about 5 g / 10 min, from about 0.005 min to about 2 g / 10 min, or from 0.005 min to about 1 g / 10 min, are contemplated in other aspects of this invention. For example, a polymer of the present invention may have a melt index in a range of 0.01 to about 10, about 0.01 to about 5, about 0.01 to about 2, about 0.01 to about 1, about 0.02 min to about 1, about 0.05 to about 2 or about 0.05 to about 0.5 g / 10 min.

The ethylene polymers produced according to this invention may have an IFAC / IF ratio greater than about 40, such as, for example, in a range between about 50 and about 500, between about 50 and about 400 or between about 50 and about 300 Other suitable ranges for the IFAC / IF ratio may include from about 60 to about 400, from about 60 to about 250, from about 50 to about 200, from about 60 to about 200, from about 70 to about 200, or about 50 to about 150, and the like, but not limited to these.

Densities of ethylene-based polymers produced using the processes and catalytic systems described herein are often greater than about 0.91 g / cm 3. In one aspect of this invention, the density of the ethylene polymer may be in a range of about 0.915 g / cm3 to about 0.965 g / cm3. Still, in another aspect, the density may be in a range of about 0.92 g / cm3 to about 0.96 g / cm3, such as, for example, from about 0.92 g / cm3 to about 0.95 g / cm3, from about 0.925 g / cm3 to about 0.955 g / cm3, or from about 0.93 g / cm3 to about 0.95 g / cm3.

Ethylene polymers such as copolymers, terpolymers, etc., consistent with various aspects of the present invention may generally have weight average molecular weights (Mp), for example, in a range of about 150,000 g / mol to about 500,000 g / mol, from approximately 200,000 g / mol to approximately 500,000 g / mol, from approximately 175,000 g / mol to approximately 400,000 g / mol, from approximately 175,000 g / mol to approximately 350,000 g / mol or approximately 200,000 g / mol to approximately 300,000 g / mol. Likewise, suitable non-limiting ranges of the number average molecular weight (Mn) may include from about 8,000 g / mol to about 30,000 g / mol, from about 8,000 g / mol to about 25,000 g / mol, from about 10,000 g / mol to approximately 25,000 g / mol, from approximately 10,000 g / mol to approximately 18,000 g / mol or from approximately 10,000 g / mol to approximately 15,000 g / mol. In addition, the average molecular weight z (Mz) of these polymers can often be greater than about 750000 g / mol and, more frequently, greater than about 1000 000 g / mol. The ranges of Mz contemplated by the present invention may include from about 750,000 g / mol to about 3,000,000 g / mol, from about 750,000 g / mol to about 2,500,000, from about 900,000 g / mol to about 2 000 000, from approximately 1000 000 g / mol to approximately 3000 000 g / mol or from approximately 1000 000 g / mol to approximately 2000000 g / mol, but not limited to these.

The ratio of Mp / Mn, or the polydispersity index, for the polymers of this invention can often be in a range of about 10 to about 40. In some aspects described herein, the Mp / Mn ratio may be in a range of about 10 to about 35, about 10 to about 30 or about 15 to about 30. In other aspects, the Mp / Mn ratio may be in a range of about 15 to about 40, from about 15 to about 35 or from about 15 to about 25. The Mz / Mp ratio for the polymers of this invention can often be in a range of about 3 to about 10. For example, the Mz / Mp ratio can be in a range of about 3 to about 9, from about 3.5 to about 9, from about 4 to about 9, or from about 4 to about 8.

The ethylene-based polymers of this invention can also be characterized as having a non-bimodal molecular weight distribution. As used herein, "non-bimodal" means that there are no two distinguishable peaks in the molecular weight distribution curve (when determined using gel permeation chromatography (GPC) or other recognized analytical technique). Non-bimodal includes unimodal distributions, where there is only one peak. The peaks are also not distinguishable if there are two peaks in the molecular weight distribution curve and there is no obvious valley between the peaks, either one of the peaks is not considered a distinguishable peak, or the two are not considered Peaks are distinguishable. Figures 1-5 illustrate representative bimodal molecular weight distribution curves (amount of material versus the logarithm of molecular weight). In these figures, there is a valley between the peaks and the peaks can be separated or deconvolved. Frequently, a bimodal molecular weight distribution is characterized by having an identifiable high molecular weight component (or distribution) and an identifiable low molecular weight component (or distribution). In contrast, Figures 6-11 illustrate representative non-bimodal molecular weight distribution curves. These include unimodal molecular weight distributions, as well as distribution curves that contain two peaks that cannot be easily distinguished, separated or deconvolved.

In addition, the ratio of the molecular weight of the polymer in D15 to the molecular weight of the polymer in D85 may be in a range of about 30 to about 90. D85 is the molecular weight at which 85% of the polymer by weight has the highest molecular weight and D15 It is the molecular weight at which 15% of the polymer by weight has the highest molecular weight. D85 and D15 are plotted in Figure 12 for a molecular weight distribution curve as a function of the logarithm increase in molecular weight. According to one aspect of the present invention, the ratio of the molecular weight of the polymer in D15 to the molecular weight of the polymer in D85 may be in a range of about 30 to about 85, or about 40 to about 90. In another aspect, this ratio may be in a range of about 40 to about 85, about 40 to about 80, about 40 to about 75, about 40 to about 70, about 35 to about 80, about 35 to about 70, or about 35 to about 60.

In general, polymers produced in aspects of the present invention have low levels of long chain branching, typically with less than about 0.01 long chain branches (RCL) per 1000 total carbon atoms, but greater than zero. In some aspects, the number of RCL per 1000 total carbon atoms may be less than about 0.008, less than about 0.007, less than about 0.005 or less than about 0.003 RCL per 1000 total carbon atoms.

The ethylene copolymers of the invention produced using the polymerization processes and catalyst systems described above have a reverse comonomer distribution, that is, a short chain branching content that increases as the molecular weight is increased, for example , the higher molecular weight components of the polymer generally have greater comonomer incorporation than the lower molecular weight components. Typically, there is an increasing comonomer incorporation with increasing molecular weight. For example, the number of short chain branches (RCC) per 1000 total carbon atoms may be greater in Mp than in Mn. In one aspect, the ratio of the number of short chain chains (RCC) per 1000 total carbon atoms of the polymer to Mp to the number of RCC per 1000 total carbon atoms of the polymer to Mn may be in a range of about 1.1 : 1 to about 5: 1, or alternatively, in a range of about 1.5: 1 to about 4: 1.

The distribution of inverse short chain branching (DRCC) or inverse comonomer distribution can be characterized by the average number of short chain branching (RCC) per 1000 total carbon atoms that is increased by each fraction of 10% by weight of polymer that it is increased from D85 to D15 (or from D80 to D10, defined similarly for D85 and D15). In one aspect, for example, the average number of RCC per 1000 total carbon atoms in the range of D80 to D70 is less than in the range of D70 to D60, which is less than in the range of D60 to D50, which is less than in the range of D50 to D40, which is less than in the range of D40 to D30, which is less than in the range of D30 to D20, which is less than in the range of D20 to D10.

In another aspect, the DRCC of the polymers of the present invention can be characterized by the ratio of the number of RCC per 1000 total carbon atoms of the polymer in D10 to the number of RCC per 1000 total carbon atoms of the polymer in D50, that is, (RCC in D10) / (RCC in D50). D50 is the molecular weight at which 50% of the polymer by weight has the highest molecular weight and D10 is the molecular weight at which 10% of the polymer by weight has the highest molecular weight. D50 and D10 are plotted in Figure 13 for a molecular weight distribution curve as a function of the logarithm increase in molecular weight. According to one aspect of the present invention, a ratio of the number of RCC per 1000 total carbon atoms of the polymer in D10 to the number of RCC per 1000 total carbon atoms of the polymer in D50 may be in a range of about 1.1 to about 10. For example, the ratio may be in a range of about 1.2 to about 10, about 1.1 to about 5, about 1.2 to about 5, about 1.5 to about 10, about 2 to about 5, or about 2 to about 4.

An illustrative and non-limiting example of an ethylene polymer of the present invention can be characterized by a melt index in a range of about 0.005 g / 10 minutes to about 10 g / 10 minutes, an IFAC / IF ratio in a range from about 50 to about 500, a density in a range of about 0.915 g / cm 3 to about 0.965 g / cm 3 and a non-bimodal molecular weight distribution. Another illustrative and non-limiting example of an ethylene polymer of the present invention can be characterized by a melt index in a range of about 0.01 g / 10 minutes to about 2 g / 10 minutes, an IFAC / IF ratio in a range of about 50 to about 200, a density in a range of about 0.925 g / cm3 to about 0.955 g / cm3 and a non-bimodal molecular weight distribution (eg, unimodal).

Ethylene polymers, whether copolymers, terpolymers, etc., can be formed into various articles of manufacture. Items that may comprise polymers of this invention include an agricultural film, a car part, a bottle, a drum, a fiber or cloth, a food packaging film or container, a food service item, a fuel tank , a geomembrane, a domestic container, a lining, a molded product, a medical material or service, a pipe, a sheet or tape, a toy and the like, but not limited to these. Several procedures can be used to form these items. Non-limiting examples of these procedures include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming and the like. Additionally, additives and modifiers are frequently added to these polymers to provide beneficial polymer treatment or attributes of end-use products. Such processes and materials are described in Modern Plastics Encyclopedia, mid-November 1995 edition, vol. 72, No. 12 and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992.

Applicants also contemplate a method of forming or preparing an article of manufacture comprising a polymer produced by any of the polymerization processes described herein. For example, a method may comprise (i) bringing a catalytic composition into contact with an olefinic monomer and an olefinic (one or more) comonomer under polymerization conditions to produce an olefinic polymer, wherein the catalytic composition may comprise (i) component Catalytic I, Catalytic Component II, Catalytic Component III, an activator (for example, an activating support comprising a solid oxide treated with an electron acceptor anion), and an optional cocatalyst (for example, an organoaluminum compound) and (ii ) forming an article of manufacture comprising the olefinic polymer. The forming step may comprise mixing, melt treatment, extrusion, molding or thermoforming and the like, including combinations thereof.

Examples

The invention is further illustrated by the following examples, which should not be construed in any way as limitations on the scope of this invention.

The melt index (IF, g / 10 min) was determined according to ASTM D1238 at 190 ° C with a weight of 2,160 grams. The high load melt index (IFAC, g / 10 min) was determined according to ASTM D1238 at 190 ° C with a weight of 21,600 grams.

The density of the polymer was determined in grams per cubic centimeter (g / cm3) in a compression molded sample, cooled to approximately 15 ° C per hour and conditioned for approximately 40 hours at room temperature according to ASTM D1505 and ASTM D1928, procedure C.

Molecular weight distributions and molecular weights were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA ) operating at 145 ° C. The mobile phase flow rate of 1,2,4-trichlorobenzene (TCB) containing 0.5 g / l of 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 ml / min and the Polymer solution concentrations were in the range of 1.0 mg / ml to 1.5 mg / ml, depending on the molecular weight. Sample preparation was carried out at 150 ° C for 4 hours nominally with occasional mild agitation before the solutions were transferred to sample vials for injection. The integral calibration method was used to deduce molecular weights and molecular weight distributions by using an HDPE polyethylene resin from Chevron Phillips Chemicals Company, MARLEX® BHB5003, as a broad standard. The comprehensive table of the broad standard was predetermined in a separate experiment with SEC-MALS.

The content of the short chain branch (RCC) and the distribution of short chain branching (DRCC) in the molecular weight distribution were determined through a GPC system with IR5 detection (IR5-GPC), where the GPC system It was a PL220 GPC / SEC system (Polymer Labs, an Agilent company) equipped with three HMW-6E Styragel columns (Waters, MA) for polymer separation. An IR5 MCT thermoelectric cooling (IR5) detector (Polymer Char, Spain) was connected to the GPC columns through a heat transfer line. Chromatographic data were obtained from two output ports of the IR5 detector. First, the analog signal is transferred from an analog output port to a digitizer before connecting computer "A" for molecular weight determinations through Cirrus software (Polymer Labs, currently an Agilent company) and the method Integral calibration using a broad Marlex ™ BHB5003 MWD HDPE resin (Chevron Phillips Chemical) as the broad molecular weight standard. On the other hand, the digital signals are transferred via a USB cable directly to the "B" computer where they are collected using LabView data collection software provided by Polymer Char. The chromatographic conditions were set as follows: oven temperature for columns of 145 ° C; flow rate of 1 ml / min; 0.4 ml injection volume and polymer concentration of approximately 2 mg / ml, depending on the molecular weight of the sample. The temperatures for the sample cell of both the heat transfer line and the IR5 detector were set at 150 ° C, while the temperature of the electronic elements of the IR5 detector was set at 60 ° C. The short chain branching content was determined through an internal method using the intensity ratio of CH3 (Ich3) to CH2 (Ich2) coupled with a calibration curve. The calibration curve was a graph of the RCC content (Xrcc) as a function of the intensity ratio of Ich3 / Ich2. To obtain a calibration curve, a group of polyethylene resins (not less than 5) of RCC level was used varying from zero to about 32 RCC / 1000 total carbons (RCC standards). All these RCC standards have known RCC levels and flat DRCC profiles predetermined separately by NMR and solvent gradient fractionation coupled with NMR methods (SGF-Nm R). By using RCC calibration curves so established, short chain branching distribution profiles were obtained by molecular weight distribution for fractionated resins using the IR5-GPC system under exactly the same chromatographic conditions as for these RCC standards. A correspondence between the intensity ratio and the elution volume was converted into the RCC distribution as a function of the DPM with a predetermined RCC calibration curve (i.e. IcH3 / IcH2 intensity ratio versus the RCC content) and the PM calibration curve (i.e. molecular weight versus elution time) to convert the intensity ratio of Ich3 / Ich2 and elution time into RCC content and molecular weight, respectively.

Long chain branches (RCL) per 1000 total carbon atoms can be determined as described in US Patent No. 8,114,946, "Diagnosing Long-Chain Branching in Polyethylenes", J. Mol. Struct.

485-486, 569-584 (1999) and J. Phys. Chem. 1980, 84, 649.

Sulfated alumina activator supports were prepared as follows. Boemite was obtained from W. R. Grace & Company with the designation "Alumina A" and with a specific surface area of approximately 300 m2 / g and a pore volume of approximately 1.3 ml / g. This material was obtained as a powder having an average particle size of approximately 100 micrometers. This material was impregnated to incipient moisture with an aqueous solution of ammonium sulfate up to about 15% sulfate. This mixture was then placed on a flat tray and allowed to dry under vacuum at approximately 110 ° C for approximately 16 hours. To calcine the resulting powder mixture, the material was fluidized in a stream of dry air at about 550 ° C for about 6 hours. Then, the sulfated alumina was collected and stored in dry nitrogen, and used without exposure to the atmosphere.

Examples 1 to 6

Examples 1 to 4 were produced using the following polymerization procedure. All polymerization runs were carried out in a 3.8 l stainless steel reactor (one gallon). Isobutane (1.8 L) was used in all runs. Metallocene solutions at approximately 1 mg / ml in toluene were prepared. Approximately 1 mmol of alkylaluminum (triisobutylaluminum), 300 mg of sulfated alumina and the metallocene solutions were added in that order through a loading port, while isobutane vapor was slowly discharged. The charging port was closed and isobutane was added. The reactor contents were stirred and heated to the desired operating temperature of approximately 95 ° C and then ethylene was introduced into the reactor with 10 g of 1-hexene and hydrogen at 300 ppm by weight of ethylene. Ethylene and hydrogen were fed on demand at the specified weight ratio to maintain the target pressure of 3 Mpa (420 psig) pressure during the 40 minute extension of the polymerization run. The reactor was maintained at the desired run temperature throughout the run by an automated heating-cooling system. The following metallocene compounds were used in examples 1 to 4:

Table I summarizes certain process conditions and properties of the polymers of Examples 1 to 6. Example 5 was an ethylene copolymer produced using a chromium base catalyst system (TR480) and example 6 was an ethylene copolymer produced using a chromium based catalyst system (TR418).

In Table I, Mn is the number average molecular weight, Mp is the weight average molecular weight, Mz is the average molecular weight in z, IF in the melt index and IFAC is the high load melt index. Table II summarizes the molecular weights of D10, D15, D50, D80 and D85 for the polymers of Examples 1 to 6 and Table III summarizes the number of short chain branches per 1000 total carbon atoms in D10 and D50 for Polymers of Examples 1 to 6. Figure 14 illustrates the molecular weight distributions of the polymers of Examples 1 to 6 and Figures 15 to 19 illustrate the short chain branching distributions of the polymers of Examples 1 to 6.

As shown in Tables I and II and in Figure 14, the polymers of Examples 1 to 4 have wide (and non-bimodal) molecular weight distributions (Mp / Mn from 16 to 21) with large flow rates (IFAC / IF from 102 to 155). The distribution of inverse comonomers and increasing levels of RCC per 1000 total carbon atoms for examples 1 to 4 are illustrated in Figures 15 to 18 and Table III and contrast with the opposite RCC profile of examples 5 to 6 illustrated. in figure 19 and table III.

Table I. Process conditions and properties of the polymers of examples 1 to 6.

Table I. Process conditions and properties of the polymers of examples 1 to 6 (continued).

Table II Certain molecular weight properties of the polymers of Examples 1 to 6.

Table III Short chain branching content of the polymers of Examples 1 to 6.

Claims (13)

1. An olefin polymer having a melt index in a range of 0.005 to 10 g / 10 min, determined according to ASTM-1238 at 190 ° C with a weight of 2,160 grams, an IFAC / IF ratio in a range of 50 to 500, where the IFAC is determined according to ASTM-1238 at 190 ° C with a weight of 21,600 grams, a density in a range of 0.915 g / cm3 to 0.965 g / cm3 determined according to ASTM-1505 and ASTM-1928, Method C, as described in the description, a non-bimodal molecular weight distribution and a reverse comonomer distribution determined both by GPC as described in the description. 2. The polymer of claim 1, wherein: a molar ratio of Mp / Mn of the polymer is in a range of 10 to 40; Y a ratio of the molecular weight of the polymer to the molecular weight at which 15% by weight of the polymer has a greater molecular weight (D15) with respect to the molecular weight of the polymer at which 85% by weight of the polymer has a greater molecular weight (D85) is in a range of 30 to 90. 3. The polymer of claim 2, wherein the polymer has a unimodal molecular weight distribution. 4. The polymer of claim 2, wherein: the melting index is in a range of 0.01 to 2 g / 10 min; the IFAC / IF ratio is in a range of 50 to 200; the density is in a range of 0.925 g / cm3 to 0.955 g / cm3; the ratio of Mp / Mn is in a range of 15 to 30; Y the ratio of the molecular weight of the polymer to the molecular weight at which 15% by weight of the polymer has greater molecular weight (D15) with respect to the molecular weight of the polymer at which 85% by weight of the polymer has greater molecular weight (D85) is in a range of 40 to 70. 5. The polymer of any one of claims 1 to 4, which is an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer or an ethylene / 1-octene copolymer. 6. The polymer of any one of claims 1 to 5, wherein the ratio of the number of short chain branches (RCC) per 1000 total carbon atoms of the polymer in Mp to the number of RCC per 1000 total carbon atoms in Mn is 1.1: 1 to 5: 1, more preferably 1.5: 1 to 4: 1 determined by the method described in the description. 7. The polymer of any one of claims 1 to 6, wherein Mz / Mw is in a range of 3 to 10. 8. The polymer of claim 1, wherein the ratio of the molecular weight of the polymer to the molecular weight at which 15% by weight of the polymer has greater molecular weight (D15) relative to the molecular weight of the polymer at the molecular weight at which 85% in Polymer weight has higher molecular weight (D85) is in a range of 30 to 90. 9. The polymer of any one of claims 1 to 8, wherein the ratio of the number of RCC per 1000 total carbon atoms of the polymer to the molecular weight at which 10% by weight of the polymer has greater molecular weight (D10) with respect to the RCC number per 1000 total carbon atoms of the polymer at the molecular weight at which 50% by weight of the polymer has the highest molecular weight (D50) is in the range of 1.1 to 10. 10. The polymer of any one of claims 1 to 9, having from more than zero to less than 0.01 long chain branches (RCL) per 1000 total carbon atoms. 11. An article comprising the polymer of any one of claims 1 to 10. 12. The article of claim 11 which is selected from an agricultural film, a car part, a bottle, a drum, a fiber or cloth, a food packaging film or container, a food service article, a tank of fuel, a geomembrane, a domestic container, a lining, a molded product, a device or medical material, a pipe, a sheet or tape and a toy. 13. A method of forming an article of claim 11 or claim 12, comprising injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion or thermoforming.